Composition of matter for use in organic light-emitting diodes

ABSTRACT

The present disclosure relates to compounds capable of emitting delayed fluorescence and uses of these compounds in organic light-emitting diodes.

RELATED APPLICATION

This application claims the benefit of priority to U.S. ProvisionalPatent Application No. 62/624,671, filed Jan. 31, 2018.

BACKGROUND

An organic light-emitting diode (OLED) is a light-emitting diode (LED)in which a film of organic compounds is placed between two conductors,which film emits light in response to excitation, such as an electriccurrent. OLEDs are useful in lightings and displays, such as televisionscreens, computer monitors, mobile phones, and tablets. A probleminherent in OLED displays is the limited lifetime of the organiccompounds. OLEDs which emit blue light, in particular, degrade at asignificantly increased rate as compared to green or red OLEDs.

OLED materials rely on the radiative decay of molecular excited states(excitons) generated by recombination of electrons and holes in a hosttransport material. The nature of excitation results in interactionsbetween electrons and holes that split the excited states into brightsinglets (with a total spin of 0) and dark triplets (with a total spinof 1). Since the recombination of electrons and holes affords astatistical mixture of four spin states (one singlet and three tripletsublevels), conventional OLEDs have a maximum theoretical efficiency of25%.

To date, OLED material design has focused on harvesting the remainingenergy from the normally dark triplets. Recent work to create efficientphosphors, which emit light from the normally dark triplet state, haveresulted in green and red OLEDs. Other colors, such as blue, however,require higher energy excited states which accelerate the degradationprocess of the OLED.

The fundamental limiting factor to the triplet-singlet transition rateis a value of the parameter |H_(fi)/ΔE_(ST)|², where H_(fi) is thecoupling energy due to hyperfine or spin-orbit interactions, and ΔE_(ST)is the energetic splitting between singlet and triplet states.Traditional phosphorescent OLEDs rely on the mixing of singlet andtriplet states due to spin-orbital (SO) interaction, increasing H_(fi),and affording a lowest emissive state shared between a heavy metal atomand an organic ligand. This results in energy harvesting from all highersinglet and triplet states, followed by phosphorescence (relativelyshort-lived emission from the excited triplet). The shortened tripletlifetime reduces triplet exciton annihilation by charges and otherexcitons. Recent work by others suggests that the limit to theperformance of phosphorescent materials has been reached.

SUMMARY

The present disclosure relates to novel materials for OLEDs. In someembodiments, these OLEDs can reach higher excitation states withoutrapid degradation. It has now been discovered that thermally activateddelayed fluorescence (TADF), which relies on minimization of ΔE_(ST) asopposed to maximization of H_(fi), can transfer population betweensinglet levels and triplet sublevels in a relevant timescale, such as,for example, 1 s-10 ms. The compounds described herein are capable ofluminescing at higher energy excitation states than compounds previouslydescribed.

In some embodiments, the present disclosure provides compounds ofFormula (I):

-   -   wherein    -   A is selected from

-   -   D and D′ are independently selected from

and

-   -   R and R′ are independently selected from F, CN, CF₃, Me, and        t-butyl.

In some embodiments, the present disclosure provides compounds ofFormula (II):

-   -   wherein    -   A is selected from

-   -   D and D′ are independently

-   -   X₁ and X₂ are independently selected from Ar and R;    -   Ar is independently selected from

-   -   R is independently selected from H, deuterium, F, CN, CF₃, Me,        i-propyl, t-butyl, SiMe₃, and SiPh₃.

In some embodiments, the present disclosure provides light-emittingmaterials comprising compounds of Formula (I) or (II).

In some embodiments, the present disclosure provides delayed fluorescentemitters comprising the compound of Formula (I) or (II).

In some embodiments, the present disclosure provides organiclight-emitting diodes (OLED) comprising compounds of Formula (I) or(II).

In some embodiments, provided herein is an organic light-emitting diode(OLED) comprising an anode, a cathode, and at least one organic layercomprising a light-emitting layer between the anode and the cathode,wherein the light-emitting layer comprises:

-   -   a host material; and a compound of Formula (I) or (II).

In some embodiments, provided herein is an organic light-emitting diode(OLED) comprising an anode, a cathode, and at least one organic layercomprising a light-emitting layer between the anode and the cathode,wherein the light-emitting layer comprises:

-   -   a host material; and    -   a compound of Formula (I) or (II);    -   wherein the compound of Formula (I) or (II) is a light-emitting        material.

In some embodiments, provided herein is an organic light-emitting diode(OLED) comprising an anode, a cathode, and at least one organic layercomprising a light-emitting layer between the anode and the cathode,wherein the light-emitting layer comprises:

-   -   a host material;    -   a compound of Formula (I) or (II); and    -   a light-emitting material which is not a compound of Formula (I)        or (II).

In some embodiments, provided herein is an organic light-emitting diode(OLED) comprising an anode, a cathode, and at least one organic layercomprising a light-emitting layer between the anode and the cathode,wherein the light-emitting layer comprises:

-   -   a compound of Formula (I) or (II); and    -   a light-emitting material which is not a compound of Formula (I)        or (II).

In some embodiments, the compounds of Formula (I) or (II) are used in ascreen or a display.

In yet another aspect, the present disclosure relates to a method ofmanufacturing an OLED display, the method comprising:

-   -   forming a barrier layer on a base substrate of a mother panel;    -   forming a plurality of display units in units of cell panels on        the barrier layer;    -   forming an encapsulation layer on each of the display units of        the cell panels; and    -   applying an organic film to an interface portion between the        cell panels.

BRIEF DESCRIPTION OF THE DRAWINGS

The FIGURE is a schematic wherein 1 denotes a substrate, 2 denotes ananode, 3 denotes a hole injection layer, 4 denotes a hole transportinglayer, 5 denotes a light-emitting layer, 6 denotes an electrontransporting layer, and 7 denotes a cathode.

DETAILED DESCRIPTION

In one aspect, the present disclosure provides compounds of Formula (I):

-   -   wherein    -   A is selected from

-   -   D and D′ are independently selected from

and

-   -   R and R′ are independently selected from F, CN, CF₃, Me, and        t-butyl.

In one aspect, the present disclosures provides compounds of Formula(II):

-   -   wherein    -   A is selected from

-   -   D and D′ are independently

-   -   X₁ and X₂ are independently selected from Ar and R;    -   Ar is independently selected from

and

-   -   R is independently selected from H, deuterium, F, CN, CF₃, Me,        i-propyl, t-butyl, SiMe₃, and SiPh₃.

The examples are provided by way of explanation of the disclosure, andnot by way of limitation of the disclosure. In fact, it will be apparentto those skilled in the art that various modification and variations canbe made in the present disclosure without departing from the scope orspirit of the disclosure. For instance, features illustrated ordescribed as part of one embodiment can be used on another embodiment toyield a still further embodiment. Thus it is intended that the presentdisclosure cover such modifications and variations as come within thescope of the appended claims and their equivalents. Other objects,features, and aspects of the present disclosure are disclosed in, or canbe derived from, the following detailed description. It is to beunderstood by one of ordinary skill in the art that the presentdiscussion is a description of exemplary embodiments only, and is not tobe construed as limiting the broader aspects of the present disclosure.

Definitions

Unless otherwise defined herein, scientific and technical terms used inthis application shall have the meanings that are commonly understood bythose of ordinary skill in the art. Generally, nomenclature used inconnection with, and techniques of, chemistry described herein, arethose well-known and commonly used in the art.

The term “acyl” is art-recognized and refers to a group represented bythe general Formula hydrocarbylC(O)—, preferably alkylC(O)—.

The term “acylamino” is art-recognized and refers to an amino groupsubstituted with an acyl group and may be represented, for example, bythe Formula hydrocarbylC(O)NH—.

The term “acyloxy” is art-recognized and refers to a group representedby the general Formula hydrocarbylC(O)O—, preferably alkylC(O)O—.

The term “alkoxy” refers to an alkyl group, having an oxygen attachedthereto. In some embodiments, an alkoxy has 1-20 carbon. In someembodiments, an alkoxy has 1-12 carbon atoms. Representative alkoxygroups include methoxy, trifluoromethoxy, ethoxy, propoxy, tert-butoxyand the like.

The term “alkoxyalkyl” refers to an alkyl group substituted with analkoxy group and may be represented by the general Formulaalkyl-O-alkyl.

The term “alkenyl”, as used herein, refers to an aliphatic groupcomprising at least one double bond and is intended to include both“unsubstituted alkenyls” and “substituted alkenyls”, the latter of whichrefers to alkenyl moieties having substituents replacing a hydrogen onone or more carbons of the alkenyl group. Typically, a straight chainedor branched alkenyl group has from 1 to about 20 carbon atoms,preferably from 1 to about 12 unless otherwise defined. Suchsubstituents may occur on one or more carbons that are included or notincluded in one or more double bonds. Moreover, such substituentsinclude all those contemplated for alkyl groups, as discussed below,except where stability is prohibitive. For example, substitution ofalkenyl groups by one or more alkyl, carbocyclyl, aryl, heterocyclyl, orheteroaryl groups is contemplated.

An “alkyl” group or “alkane” is a straight chained or branchednon-aromatic hydrocarbon which is completely saturated. Typically, astraight chained or branched alkyl group has from 1 to about 20 carbonatoms, preferably from 1 to about 12 unless otherwise defined. In someembodiments, the alkyl group has from 1 to 8 carbon atoms, from 1 to 6carbon atoms, from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms.Examples of straight chained and branched alkyl groups include methyl,ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl,hexyl, pentyl and octyl.

Moreover, the term “alkyl” as used throughout the specification,examples, and claims is intended to include both “unsubstituted alkyls”and “substituted alkyls”, the latter of which refers to alkyl moietieshaving substituents replacing a hydrogen on one or more substitutablecarbons of the hydrocarbon backbone. Such substituents, if not otherwisespecified, can include, for example, a halogen (e.g., fluoro), ahydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl,or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or athioformate), an alkoxy, a phosphoryl, a phosphate, a phosphonate, aphosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro,an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, asulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, an aralkyl, or anaromatic or heteroaromatic moiety. In preferred embodiments, thesubstituents on substituted alkyls are selected from C₁₋₆ alkyl, C₃₋₆cycloalkyl, halogen, carbonyl, cyano, or hydroxyl. In more preferredembodiments, the substituents on substituted alkyls are selected fromfluoro, carbonyl, cyano, or hydroxyl. It will be understood by thoseskilled in the art that the moieties substituted on the hydrocarbonchain can themselves be substituted, if appropriate. For instance, thesubstituents of a substituted alkyl may include substituted andunsubstituted forms of amino, azido, imino, amido, phosphoryl (includingphosphonate and phosphinate), sulfonyl (including sulfate, sulfonamido,sulfamoyl and sulfonate), and silyl groups, as well as ethers,alkylthios, carbonyls (including ketones, aldehydes, carboxylates, andesters), —CF₃, —CN and the like. Exemplary substituted alkyls aredescribed below. Cycloalkyls can be further substituted with alkyls,alkenyls, alkoxys, alkylthios, aminoalkyls, carbonyl-substituted alkyls,—CF₃, —CN, and the like.

The term “C_(x-y)” when used in conjunction with a chemical moiety, suchas, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant toinclude groups that contain from x to y carbons in the chain. Forexample, the term “C_(x-y) alkyl” refers to substituted or unsubstitutedsaturated hydrocarbon groups, including straight-chain alkyl andbranched-chain alkyl groups that contain from x to y carbons in thechain, including haloalkyl groups. Preferred haloalkyl groups includetrifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, andpentafluoroethyl. C₀ alkyl indicates a hydrogen where the group is in aterminal position, a bond if internal. The terms “C_(2-y) alkenyl” and“C_(2-y) alkynyl” refer to substituted or unsubstituted unsaturatedaliphatic groups analogous in length and possible substitution to thealkyls described above, but that contain at least one double or triplebond respectively.

The term “alkylamino”, as used herein, refers to an amino groupsubstituted with at least one alkyl group.

The term “alkylthio”, as used herein, refers to a thiol groupsubstituted with an alkyl group and may be represented by the generalformula alkylS—.

The term “arylthio”, as used herein, refers to a thiol group substitutedwith an aryl group and may be represented by the general formula arylS—.

The term “alkynyl”, as used herein, refers to an aliphatic groupcomprising at least one triple bond and is intended to include both“unsubstituted alkynyls” and “substituted alkynyls”, the latter of whichrefers to alkynyl moieties having substituents replacing a hydrogen onone or more carbons of the alkynyl group. Typically, a straight chainedor branched alkynyl group has from 1 to about 20 carbon atoms,preferably from 1 to about 10 unless otherwise defined. Suchsubstituents may occur on one or more carbons that are included or notincluded in one or more triple bonds. Moreover, such substituentsinclude all those contemplated for alkyl groups, as discussed above,except where stability is prohibitive. For example, substitution ofalkynyl groups by one or more alkyl, carbocyclyl, aryl, heterocyclyl, orheteroaryl groups is contemplated.

The term “amide”, as used herein, refers to a group

wherein each R^(A) independently represent a hydrogen or hydrocarbylgroup, or two R^(A) are taken together with the N atom to which they areattached complete a heterocycle having from 4 to 8 atoms in the ringstructure.

The terms “amine” and “amino” are art-recognized and refer to bothunsubstituted and substituted amines and salts thereof, e.g., a moietythat can be represented by

wherein each R^(A) independently represents a hydrogen or a hydrocarbylgroup, or two R^(A) are taken together with the N atom to which they areattached complete a heterocycle having from 4 to 8 atoms in the ringstructure.

The term “aminoalkyl”, as used herein, refers to an alkyl groupsubstituted with an amino group.

The term “aralkyl”, as used herein, refers to an alkyl group substitutedwith an aryl group.

The term “aryl” as used herein include substituted or unsubstitutedsingle-ring aromatic groups in which each atom of the ring is carbon.Preferably the ring is a 6- or 20-membered ring, more preferably a6-membered ring. Preferably an aryl has 6-40 carbon atoms, morepreferably has 6-25 carbon atoms. The term “aryl” also includespolycyclic ring systems having two or more cyclic rings in which two ormore carbons are common to two adjoining rings wherein at least one ofthe rings is aromatic, e.g., the other cyclic rings can be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline,and the like.

The term “carbamate” is art-recognized and refers to a group

wherein each R^(A) independently represent hydrogen or a hydrocarbylgroup, such as an alkyl group, or both R^(A) taken together with theintervening atom(s) complete a heterocycle having from 4 to 8 atoms inthe ring structure.

The terms “carbocycle”, and “carbocyclic”, as used herein, refers to asaturated or unsaturated ring in which each atom of the ring is carbon.Preferably, a carbocylic group has from 3 to 20 carbon atoms. The termcarbocycle includes both aromatic carbocycles and non-aromaticcarbocycles. Non-aromatic carbocycles include both cycloalkane rings, inwhich all carbon atoms are saturated, and cycloalkene rings, whichcontain at least one double bond. “Carbocycle” includes 5-7 memberedmonocyclic and 8-12 membered bicyclic rings. Each ring of a bicycliccarbocycle may be selected from saturated, unsaturated and aromaticrings. Carbocycle includes bicyclic molecules in which one, two or threeor more atoms are shared between the two rings. The term “fusedcarbocycle” refers to a bicyclic carbocycle in which each of the ringsshares two adjacent atoms with the other ring. Each ring of a fusedcarbocycle may be selected from saturated, unsaturated and aromaticrings. In an exemplary embodiment, an aromatic ring, e.g., phenyl (Ph),may be fused to a saturated or unsaturated ring, e.g., cyclohexane,cyclopentane, or cyclohexene. Any combination of saturated, unsaturatedand aromatic bicyclic rings, as valence permits, is included in thedefinition of carbocyclic. Exemplary “carbocycles” include cyclopentane,cyclohexane, bicyclo[2.2.1]heptane, 1,5-cyclooctadiene,1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]oct-3-ene, naphthalene andadamantane. Exemplary fused carbocycles include decalin, naphthalene,1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane,4,5,6,7-tetrahydro-1H-indene and bicyclo[4.1.0]hept-3-ene. “Carbocycles”may be substituted at any one or more positions capable of bearing ahydrogen atom.

A “cycloalkyl” group is a cyclic hydrocarbon which is completelysaturated. “Cycloalkyl” includes monocyclic and bicyclic rings.Preferably, a cycloalkyl group has from 3 to 20 carbon atoms. Typically,a monocyclic cycloalkyl group has from 3 to about 10 carbon atoms, moretypically 3 to 8 carbon atoms unless otherwise defined. The second ringof a bicyclic cycloalkyl may be selected from saturated, unsaturated andaromatic rings. Cycloalkyl includes bicyclic molecules in which one, twoor three or more atoms are shared between the two rings. The term “fusedcycloalkyl” refers to a bicyclic cycloalkyl in which each of the ringsshares two adjacent atoms with the other ring. The second ring of afused bicyclic cycloalkyl may be selected from saturated, unsaturatedand aromatic rings. A “cycloalkenyl” group is a cyclic hydrocarboncomprising one or more double bonds.

The term “carbocyclylalkyl”, as used herein, refers to an alkyl groupsubstituted with a carbocycle group.

The term “carbonate”, as used herein, refers to a group —OCO₂—R^(A),wherein R^(A) represents a hydrocarbyl group.

The term “carboxy”, as used herein, refers to a group represented by theFormula —CO₂H.

The term “ester”, as used herein, refers to a group —C(O)OR^(A) whereinR^(A) represents a hydrocarbyl group.

The term “ether”, as used herein, refers to a hydrocarbyl group linkedthrough an oxygen to another hydrocarbyl group. Accordingly, an ethersubstituent of a hydrocarbyl group may be hydrocarbyl-O—. Ethers may beeither symmetrical or unsymmetrical. Examples of ethers include, but arenot limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethersinclude “alkoxyalkyl” groups, which may be represented by the generalFormula alkyl-O-alkyl.

The terms “halo” and “halogen” as used herein means halogen and includeschloro, fluoro, bromo, and iodo.

The terms “hetaralkyl” and “heteroaralkyl”, as used herein, refers to analkyl group substituted with a hetaryl group.

The term “heteroalkyl”, as used herein, refers to a saturated orunsaturated chain of carbon atoms and at least one heteroatom, whereinno two heteroatoms are adjacent.

The terms “heteroaryl” and “hetaryl” include substituted orunsubstituted aromatic single ring structures, preferably 5- to20-membered rings, more preferably 5- to 6-membered rings, whose ringstructures include at least one heteroatom, preferably one to fourheteroatoms, more preferably one or two heteroatoms. Preferably aheteroaryl has 2-40 carbon atoms, more preferably has 2-25 carbon atoms.The terms “heteroaryl” and “hetaryl” also include polycyclic ringsystems having two or more cyclic rings in which two or more carbons arecommon to two adjoining rings wherein at least one of the rings isheteroaromatic, e.g., the other cyclic rings can be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.Heteroaryl groups include, for example, pyrrole, furan, thiophene,imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine,pyrimidine, and carbazole, and the like.

The term “aryloxy” refers to an aryl group, having an oxygen attachedthereto. Preferably an aryloxy has 6-40 carbon atoms, more preferablyhas 6-25 carbon atoms.

The term “heteroaryloxy” refers to an aryl group, having an oxygenattached thereto. Preferably a heteroaryloxy has 3-40 carbon atoms, morepreferably has 3-25 carbon atoms.

The term “heteroatom” as used herein means an atom of any element otherthan carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, andsulfur.

The terms “heterocyclyl”, “heterocycle”, and “heterocyclic” refer tosubstituted or unsubstituted non-aromatic ring structures, preferably 3-to 20-membered rings, more preferably 3- to 7-membered rings, whose ringstructures include at least one heteroatom, preferably one to fourheteroatoms, more preferably one or two heteroatoms. The terms“heterocyclyl” and “heterocyclic” also include polycyclic ring systemshaving two or more cyclic rings in which two or more carbons are commonto two adjoining rings wherein at least one of the rings isheterocyclic, e.g., the other cyclic rings can be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.Heterocyclyl groups include, for example, piperidine, piperazine,pyrrolidine, morpholine, lactones, lactams, and the like.

The term “heterocyclylalkyl”, as used herein, refers to an alkyl groupsubstituted with a heterocycle group.

The term “hydrocarbyl”, as used herein, refers to a group that is bondedthrough a carbon atom, wherein that carbon atom does not have a ═O or ═Ssubstituent. Hydrocarbyls may optionally include heteroatoms.Hydrocarbyl groups include, but are not limited to, alkyl, alkenyl,alkynyl, alkoxyalkyl, aminoalkyl, aralkyl, aryl, aralkyl, carbocyclyl,cycloalkyl, carbocyclylalkyl, heteroaralkyl, heteroaryl groups bondedthrough a carbon atom, heterocyclyl groups bonded through a carbon atom,heterocyclylakyl, or hydroxyalkyl. Thus, groups like methyl,ethoxyethyl, 2-pyridyl, and trifluoromethyl are hydrocarbyl groups, butsubstituents such as acetyl (which has a ═O substituent on the linkingcarbon) and ethoxy (which is linked through oxygen, not carbon) are not.

The term “hydroxyalkyl”, as used herein, refers to an alkyl groupsubstituted with a hydroxy group.

The term “lower” when used in conjunction with a chemical moiety, suchas, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant toinclude groups where there are six or fewer non-hydrogen atoms in thesubstituent. A “lower alkyl”, for example, refers to an alkyl group thatcontains six or fewer carbon atoms. In some embodiments, the alkyl grouphas from 1 to 6 carbon atoms, from 1 to 4 carbon atoms, or from 1 to 3carbon atoms. In certain embodiments, acyl, acyloxy, alkyl, alkenyl,alkynyl, or alkoxy substituents defined herein are respectively loweracyl, lower acyloxy, lower alkyl, lower alkenyl, lower alkynyl, or loweralkoxy, whether they appear alone or in combination with othersubstituents, such as in the recitations hydroxyalkyl and aralkyl (inwhich case, for example, the atoms within the aryl group are not countedwhen counting the carbon atoms in the alkyl substituent).

The terms “polycyclyl”, “polycycle”, and “polycyclic” refer to two ormore rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls,heteroaryls, and/or heterocyclyls) in which two or more atoms are commonto two adjoining rings, e.g., the rings are “fused rings”. Each of therings of the polycycle can be substituted or unsubstituted. In certainembodiments, each ring of the polycycle contains from 3 to 10 atoms inthe ring, preferably from 5 to 7.

In the phrase “poly(meta-phenylene oxides)”, the term “phenylene” refersinclusively to 6-membered aryl or 6-membered heteroaryl moieties.Exemplary poly(meta-phenylene oxides) are described in the first throughtwentieth aspects of the present disclosure.

The term “silyl” refers to a silicon moiety with three hydrocarbylmoieties attached thereto.

The term “substituted” refers to moieties having substituents replacinga hydrogen on one or more carbons of the backbone. It will be understoodthat “substitution” or “substituted with” includes the implicit provisothat such substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., which does not spontaneously undergotransformation such as by rearrangement, cyclization, elimination, etc.Moieties that may be substituted can include any appropriatesubstituents described herein, for example, acyl, acylamino, acyloxy,alkoxy, alkoxyalkyl, alkenyl, alkyl, alkylamino, alkylthio, arylthio,alkynyl, amide, amino, aminoalkyl, aralkyl, carbamate, carbocyclyl,cycloalkyl, carbocyclylalkyl, carbonate, ester, ether, heteroaralkyl,heterocyclyl, heterocyclylalkyl, hydrocarbyl, silyl, sulfone, orthioether. As used herein, the term “substituted” is contemplated toinclude all permissible substituents of organic compounds. In a broadaspect, the permissible substituents include acyclic and cyclic,branched and unbranched, carbocyclic and heterocyclic, aromatic andnon-aromatic substituents of organic compounds. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. For purposes of this invention, theheteroatoms such as nitrogen may have hydrogen and/or any permissiblesubstituents of organic compounds described herein which satisfy thevalences of the heteroatoms. Substituents can include any substituentsdescribed herein, for example, a halogen, a hydroxyl, a carbonyl (suchas a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl(such as a thioester, a thioacetate, or a thioformate), an alkoxy, aphosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, anamido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl,an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, asulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromaticmoiety. In preferred embodiments, the substituents on substituted alkylsare selected from C₁₋₆ alkyl, C₃₋₆ cycloalkyl, halogen, carbonyl, cyano,or hydroxyl. In more preferred embodiments, the substituents onsubstituted alkyls are selected from fluoro, carbonyl, cyano, orhydroxyl. It will be understood by those skilled in the art thatsubstituents can themselves be substituted, if appropriate. Unlessspecifically stated as “unsubstituted,” references to chemical moietiesherein are understood to include substituted variants. For example,reference to an “aryl” group or moiety implicitly includes bothsubstituted and unsubstituted variants.

The term “sulfonate” is art-recognized and refers to the group SO₃H, ora pharmaceutically acceptable salt thereof.

The term “sulfone” is art-recognized and refers to the group—S(O)₂—R^(A), wherein R^(A) represents a hydrocarbyl.

The term “thioether”, as used herein, is equivalent to an ether, whereinthe oxygen is replaced with a sulfur.

The term “symmetrical molecule,” as used herein, refers to moleculesthat are group symmetric or synthetic symmetric. The term “groupsymmetric,” as used herein, refers to molecules that have symmetryaccording to the group theory of molecular symmetry. The term “syntheticsymmetric,” as used herein, refers to molecules that are selected suchthat no regioselective synthetic strategy is required.

The term “donor,” as used herein, refers to a molecular fragment thatcan be used in organic light-emitting diodes and is likely to donateelectrons from its highest occupied molecular orbital to an acceptorupon excitation. In preferred embodiments, donors contain substitutedamino groups. In an example embodiment, donors have an ionizationpotential greater than or equal to −6.5 eV.

The term “acceptor,” as used herein, refers to a molecular fragment thatcan be used in organic light-emitting diodes and is likely to acceptelectrons into its lowest unoccupied molecular orbital from a donor thathas been subject to excitation. In an example embodiment, acceptors havean electron affinity less than or equal to −0.5 eV.

The term “linker,” or “bridge,” as used herein, refers to a molecularfragment that can be included in a molecule which is covalently linkedbetween acceptor and donor moieties. The linker can, for example, befurther conjugated to the acceptor moiety, the donor moiety, or both.Without being bound to any particular theory, it is believed that thelinker moiety can sterically restrict the acceptor and donor moietiesinto a specific configuration, thereby preventing the overlap betweenthe conjugated a system of donor and acceptor moieties. Examples ofsuitable linker moieties include phenyl, ethenyl, and ethynyl.

The term “multivalent,” as used herein, refers to a molecular fragmentthat is connected to at least two other molecular fragments. Forexample, a linker moiety, is multivalent.

“

” or “*” as used herein, refers to a point of attachment between twoatoms.

“Hole transport layer (HTL)” and like terms mean a layer made from amaterial which transports holes. High hole mobility is recommended. TheHTL is used to help block passage of electrons transported by theemitting layer. Low electron affinity is typically required to blockelectrons. The HTL should desirably have larger triplets to blockexciton migrations from an adjacent emisse layer (EML). Examples of HTLcompounds include, but are not limited to,di(p-tolyl)aminophenyl]cyclohexane (TAPC),N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4-diamine (TPD), andN,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB,α-NPD).

“Emitting layer” and like terms mean a layer which emits light. In someembodiments, the emitting layer comprises host material and guestmaterial. The guest material can also be referred to as a dopantmaterial, but the disclosure is not limited there to. The host materialor “host” could be bipolar or unipolar, and may be used alone or bycombination of two or more host materials. The opto-electricalproperties of the host material may differ to which type of guestmaterial (TADF, Phosphorescent or Fluorescent) is used. For Fluorescentguest materials, the host materials should have good spectral overlapbetween absorption of the guest material and emission of the material toinduce good Forster transfer to guest materials. For Phosphorescentguest materials, the host materials should have high triplet energy toconfine triplets of the guest material. For TADF guest materials, thehost materials should have both spectral overlap and higher tripletenergy.

“Dopant” and like terms, refer to additive materials for carriertransporting layers, emitting layers or other layers. In carriertransporting layers, dopant and like terms perform as an electronacceptor or a donator that increases the conductivity of an organiclayer of an organic electronic device, when added to the organic layeras an additive. Organic semiconductors may likewise be influenced, withregard to their electrical conductivity, by doping. Such organicsemiconducting matrix materials may be made up either of compounds withelectron-donor properties or of compounds with electron-acceptorproperties. In emitting layers, dopant and like terms also mean thelight-emitting material which is dispersed in a matrix, for example, ahost. When a triplet harvesting material is doped into an emitting layeror contained in an adjacent layer so as to improve exciton generationefficiency, it is named as assistant dopant. The content of theassistant dopant in the light-emitting layer or the adjacent layer isnot particularly limited so as the triplet harvesting material improvesthe exciton generation efficiency. The content of the assistant dopantin the light-emitting layer is preferably higher than, more preferablyat least twice than the light-emitting material. In the light-emittinglayer, the content of the host material is preferably 50% by weight ormore, the content of the assistant dopant is preferably from 5% byweight to less than 50% by weight, and the content of the light-emittingmaterial is preferably more than 0% by weight to less than 25% byweight, more preferably from 0% by weight to less than 10% by weight.The content of the assistant dopant in the adjacent layer may be morethan 50% by weight and may be 100% by weight. In the case where a devicecontaining a triplet harvesting material in a light-emitting layer or anadjacent layer has a higher light emission efficiency than a devicewithout the triplet harvesting material, such triplet harvestingmaterial functions as an assistant dopant. A light-emitting layercontaining a host material, an assistant dopant and a light-emittingmaterial satisfies the following (A) and preferably satisfies thefollowing (B):ES1(A)>ES1(B)>ES1(C)  (A)ET1(A)>ET1(B)  (B)

wherein ES1(A) represents a lowest excited singlet energy level of thehost material; ES1(B) represents a lowest excited singlet energy levelof the assistant dopant; ES1(C) represents a lowest excited singletenergy level of the light-emitting material; ET1(A) represents a lowestexcited triplet energy level at 77 K of the host material; and ET1(B)represents a lowest excited triplet energy level at 77 K of theassistant dopant. The assistant dopant has an energy difference ΔEstbetween a lowest singlet excited state and a lowest triplet excitedstate at 77 K of preferably 0.3 eV or less, more preferably 0.2 eV orless, still more preferably 0.1 eV or less.

In the compounds of this invention any atom not specifically designatedas a particular isotope is meant to represent any stable isotope of thatatom. Unless otherwise stated, when a position is designatedspecifically as “H” or “hydrogen”, the position is understood to havehydrogen at its natural abundance isotopic composition. Also unlessotherwise stated, when a position is designated specifically as“deuterium”, the position is understood to have deuterium at anabundance that is at least 3340 times greater than the natural abundanceof deuterium, which is 0.015% (i.e., at least 50.1% incorporation ofdeuterium).

“d” refers to deuterium.

“Substituted with deuterium” refers to the replacement of one or morehydrogen atoms with a corresponding number of deuterium atoms.

The term “isotopic enrichment factor” as used herein means the ratiobetween the isotopic abundance and the natural abundance of a specifiedisotope.

In various embodiments, compounds of this invention have an isotopicenrichment factor for each designated deuterium atom of at least 3500(52.5% deuterium incorporation at each designated deuterium atom), atleast 4000 (60% deuterium incorporation), at least 4500 (67.5% deuteriumincorporation), at least 5000 (75% deuterium), at least 5500 (82.5%deuterium incorporation), at least 6000 (90′/o deuterium incorporation),at least 6333.3 (95% deuterium incorporation), at least 6466.7 (97%deuterium incorporation), at least 6600 (99% deuterium incorporation),or at least 6633.3 (99.5% deuterium incorporation).

The term “isotopologue” refers to a species that differs from a specificcompound of this invention only in the isotopic composition thereof.

The term “compound,” when referring to a compound of this invention,refers to a collection of molecules having an identical chemicalstructure, except that there may be isotopic variation among theconstituent atoms of the molecules. Thus, it will be clear to those ofskill in the art that a compound represented by a particular chemicalstructure containing indicated deuterium atoms, will also contain lesseramounts of isotopologues having hydrogen atoms at one or more of thedesignated deuterium positions in that structure. The relative amount ofsuch isotopologues in a compound of this invention will depend upon anumber of factors including the isotopic purity of deuterated reagentsused to make the compound and the efficiency of incorporation ofdeuterium in the various synthesis steps used to prepare the compound.However, as set forth above the relative amount of such isotopologues intoto will be less than 49.9% of the compound. In other embodiments, therelative amount of such isotopologues in toto will be less than 47.5%,less than 40%, less than 32.5%, less than 25%, less than 17.5%, lessthan 10%, less than 5%, less than 3%, less than 1%, or less than 0.5% ofthe compound.

Principles of OLED

OLEDs are typically composed of a layer of organic materials orcompounds between two electrodes, an anode and a cathode. The organicmolecules are electrically conductive as a result of delocalization of πelectronics caused by conjugation over part or all of the molecule. Whenvoltage is applied, electrons from the highest occupied molecularorbital (HOMO) present at the anode flow into the lowest unoccupiedmolecular orbital (LUMO) of the organic molecules present at thecathode. Removal of electrons from the HOMO is also referred to asinserting electron holes into the HOMO. Electrostatic forces bring theelectrons and the holes towards each other until they recombine and forman exciton (which is the bound state of the electron and the hole). Asthe excited state decays and the energy levels of the electrons relax,radiation having a frequency in the visible spectrum is emitted. Thefrequency of this radiation depends on the band gap of the material,which is the difference in energy between the HOMO and the LUMO.

As electrons and holes are fermions with half integer spin, an excitonmay either be in a singlet state or a triplet state depending on how thespins of the electron and hole have been combined. Statistically, threetriplet excitons will be formed for each singlet exciton. Decay fromtriplet states is spin forbidden, which results in increases in thetimescale of the transition and limits the internal efficiency offluorescent devices. Phosphorescent organic light-emitting diodes makeuse of spin-orbit interactions to facilitate intersystem crossingbetween singlet and triplet states, thus obtaining emission from bothsinglet and triplet states and improving the internal efficiency.

One prototypical phosphorescent material is iridiumtris(2-phenylpyridine) (Ir(ppy)₃) in which the excited state is a chargetransfer from the Ir atom to the organic ligand. Such approaches havereduced the triplet lifetime to about several is, several orders ofmagnitude slower than the radiative lifetimes of fully-allowedtransitions such as fluorescence. Ir-based phosphors have proven to beacceptable for many display applications, but losses due to largetriplet densities still prevent the application of OLEDs to solid-statelighting at higher brightness.

TADF seeks to minimize ΔE_(ST). The reduction in exchange splitting fromtypical values of 0.4-0.7 eV to a gap of the order of the thermal energy(proportional to kBT, where kB represents the Boltzmann constant, and Trepresents temperature) means that thermal agitation can transferpopulation between singlet levels and triplet sublevels in a relevanttimescale even if the coupling between states is small.

TADF molecules consist of donor and acceptor moieties connected directlyby a covalent bond or via a conjugated linker (or “bridge”). A “donor”moiety is likely to transfer electrons from its HOMO upon excitation tothe “acceptor” moiety. An “acceptor” moiety is likely to accept theelectrons from the “donor” moiety into its LUMO. The donor-acceptornature of TADF molecules results in low-lying excited states withcharge-transfer character that exhibit very low ΔE_(ST). Since thermalmolecular motions can randomly vary the optical properties ofdonor-acceptor systems, a rigid three-dimensional arrangement of donorand acceptor moieties can be used to limit the non-radiative decay ofthe charge-transfer state by internal conversion during the lifetime ofthe excitation.

It is beneficial, therefore, to decrease ΔE_(ST), and to create a systemwith increased reversed intersystem crossing (RISC) capable ofexploiting triplet excitons. Such a system, it is believed, will resultin increased quantum efficiency and decreased emission lifetimes.Systems with these features will be capable of emitting light withoutbeing subject to the rapid degradation prevalent in OLEDs known today.

Compounds of the Disclosure

In some embodiments, the compounds have a structure of Formula (I):

-   -   wherein    -   A is selected from

-   -   D and D′ are independently selected from

and

-   -   R and R′ are independently selected from F, CN, CF₃, Me, and        t-butyl.

In some embodiments, A is A1. In some embodiments, A is A2. In someembodiments, A is A3. In some embodiments, A is A4. In some embodiments,A is A5. In some embodiments, A is A1 or A3.

In some embodiments, D is D1. In some embodiments, D is D2. In someembodiments, D is D3. In some embodiments, D is D4. In some embodiments,D is D5. In some embodiments, D is D6. In some embodiments, D is D7. Insome embodiments, D is D8. In some embodiments, D is D9. In someembodiments, D is D10. In some embodiments, D is D11. In someembodiments, D is D12. In some embodiments, D is D13. In someembodiments, D is D14. In some embodiments, D is D15. In someembodiments, D is D16. In some embodiments, D is D17. In someembodiments, D is D18. In some embodiments, D is D19. In someembodiments, D is D20. In some embodiments, D is D21. In someembodiments, D is D22. In some embodiments, D is D23. In someembodiments, D is D24. In some embodiments, D is D25. In someembodiments, D is D26. In some embodiments, D is D27. In someembodiments, D is D28. In some embodiments, D is D29. In someembodiments, D is D30. In some embodiments, D is D31. In someembodiments, D is D32. In some embodiments, D is D33. In someembodiments, D is D34. In some embodiments, D is D35. In someembodiments, D is D36. In some embodiments, D is D37. In someembodiments, D is D38. In some embodiments, D is D39. In someembodiments, D is D40. In some embodiments, D is D41. In someembodiments, D is D42. In some embodiments, D is D43. In someembodiments, D is D44. In some embodiments, D is D45. In someembodiments, D is D46. In some embodiments, D is D47.

In some embodiments, D is selected from D1, D2, D3, D4, D5, D6, and D7.In some embodiments, D is selected from D8, D9, D10, D11, D12, and D13.In some embodiments, D is selected from D14, D15, and D16. In someembodiments, D is selected from D17, D18, and D19. In some embodiments,D is selected from D20, D21, D22, D23, and D24. In some embodiments, Dis selected from D25, D26, and D27. In some embodiments, D is selectedfrom D28, D29, D30, and D31. In some embodiments, D is selected fromD32, D33, D34, and D35. In some embodiments, D is selected from D36,D37, D38, and D39. In some embodiments, D is selected from D40, D41,D42, and D43. In some embodiments, D is selected from D44 and D45. Insome embodiments, D is selected from D46 and D47.

In some embodiments, D′ is D1. In some embodiments, D′ is D2. In someembodiments, D′ is D3. In some embodiments, D′ is D4. In someembodiments, D′ is D5. In some embodiments, D′ is D6. In someembodiments, D′ is D7. In some embodiments, D′ is D8. In someembodiments, D′ is D9. In some embodiments, D′ is D10. In someembodiments, D′ is D11. In some embodiments, D′ is D12. In someembodiments, D′ is D13. In some embodiments, D′ is D14. In someembodiments, D′ is D15. In some embodiments, D′ is D16. In someembodiments, D′ is D17. In some embodiments, D′ is D18. In someembodiments, D′ is D19. In some embodiments, D′ is D20. In someembodiments, D′ is D21. In some embodiments, D′ is D22. In someembodiments, D′ is D23. In some embodiments, D′ is D24. In someembodiments, D′ is D25. In some embodiments, D′ is D26. In someembodiments, D′ is D27. In some embodiments, D′ is D28. In someembodiments, D′ is D29. In some embodiments, D′ is D30. In someembodiments, D′ is D31. In some embodiments, D′ is D32. In someembodiments, D′ is D33. In some embodiments, D′ is D34. In someembodiments, D′ is D35. In some embodiments, D′ is D36. In someembodiments, D′ is D37. In some embodiments, D′ is D38. In someembodiments, D′ is D39. In some embodiments, D′ is D40. In someembodiments, D′ is D41. In some embodiments, D′ is D42. In someembodiments, D′ is D43. In some embodiments, D′ is D44. In someembodiments, D′ is D45. In some embodiments, D′ is D46. In someembodiments, D′ is D47.

In some embodiments, D′ is selected from D1, D2, D3, D4, D5, D6, and D7.In some embodiments, D′ is selected from D8, D9, D10, D11, D12, and D13.In some embodiments, D′ is selected from D14, D15, and D16. In someembodiments, D′ is selected from D17, D18, and D19. In some embodiments,D′ is selected from D20, D21, D22, D23, and D24. In some embodiments, D′is selected from D25, D26, and D27. In some embodiments, D′ is selectedfrom D28, D29, D30, and D31. In some embodiments, D′ is selected fromD32, D33, D34, and D35. In some embodiments, D′ is selected from D36,D37, D38, and D39. In some embodiments, D′ is selected from D40, D41,D42, and D43. In some embodiments, D′ is selected from D44 and D45. Insome embodiments, D′ is selected from D46 and D47.

In some embodiments, R is F. In some embodiments, R is CN. In someembodiments, R is CF₃. In some embodiments, R is Me. In someembodiments, R is t-butyl.

In some embodiments, R′ is F. In some embodiments, R′ is CN. In someembodiments, R′ is CF₃. In some embodiments, R′ is Me. In someembodiments, R′ is t-butyl.

In some embodiments, R and R′ are the same. In some embodiments, R andR′ are different.

In some embodiments, the compounds have a structure of Formula (II):

-   -   wherein    -   A is selected from

-   -   D and D′ are independently

-   -   X₁ and X₂ are independently selected from Ar and R;    -   Ar is independently selected from

and

-   -   R is independently selected from H, deuterium, F, CN, CF₃, Me,        i-propyl, t-butyl, SiMe₃, and SiPh₃.

In some embodiments, A is A1. In some embodiments, A is A2. In someembodiments, A is A3. In some embodiments, A is A4. In some embodiments,A is A5. In some embodiments, A is A1 or A3.

In some embodiments, D and D′ are the same. In some embodiments, D andD′ are different.

In some embodiments, X₁ is Ar. In some embodiments, X₁ is R.

In some embodiments, X₂ is Ar. In some embodiments, X₂ is R.

In some embodiments, X₁ and X₂ are the same. In some embodiments, X₁ andX₂ are different.

In some embodiments, Ar is Ar1. In some embodiments, Ar is Ar2. In someembodiments, Ar is Ar3. In some embodiments, Ar is Ar4. In someembodiments, D is D5. In some embodiments, Ar is Ar6. In someembodiments, Ar is Ar7. In some embodiments, Ar is Ar8. In someembodiments, Ar is Ar9. In some embodiments, Ar is Ar10. In someembodiments, Ar is Ar11. In some embodiments, Ar is Ar12. In someembodiments, Ar is Ar13. In some embodiments, Ar is Ar14. In someembodiments, Ar is Ar15. In some embodiments, Ar is Ar16. In someembodiments, Ar is Ar17. In some embodiments, Ar is Ar18. In someembodiments, Ar is Ar19. In some embodiments, Ar is Ar20. In someembodiments, Ar is Ar21. In some embodiments, Ar is Ar22. In someembodiments, Ar is Ar23. In some embodiments, Ar is Ar24. In someembodiments, Ar is Ar25. In some embodiments, Ar is Ar26. In someembodiments, Ar is Ar27. In some embodiments, Ar is Ar28. In someembodiments, Ar is Ar29. In some embodiments, Ar is Ar30. In someembodiments, Ar is Ar31. In some embodiments, Ar is Ar32. In someembodiments, Ar is Ar33. In some embodiments, Ar is Ar34. In someembodiments, Ar is Ar35. In some embodiments, Ar is Ar36. In someembodiments, Ar is Ar37. In some embodiments, Ar is Ar38. In someembodiments, Ar is Ar39. In some embodiments, Ar is Ar40. In someembodiments, Ar is Ar41. In some embodiments, Ar is Ar42. In someembodiments, Ar is Ar43.

In some embodiments, Ar is selected from Ar1, Ar2, Ar3, Ar4, Ar5, D6,Ar7, Ar8, Ar9, and Ar10. In some embodiments, Ar is selected from Ar11,Ar12, Ar13, Ar14, Ar15, and Ar16. In some embodiments, Ar is selectedfrom Ar17, Ar18, and Ar19. In some embodiments, Ar is selected fromAr20, Ar21, Ar22, Ar23, and Ar24. In some embodiments, Ar is selectedfrom Ar25, Ar26, and Ar27. In some embodiments, Ar is selected fromAr28, Ar29, Ar30, and Ar31. In some embodiments, Ar is selected fromAr32, Ar33, Ar34, and Ar35. In some embodiments, D′ is selected fromAr36, Ar37, Ar38, and Ar39. In some embodiments, Ar is selected fromAr40, Ar41, Ar42 and Ar43.

In some embodiments, R is H. In some embodiments, R is deuterium. Insome embodiments, R is F. In some embodiments, R is CN. In someembodiments, R is CF₃. In some embodiments, R is Me. In someembodiments, R is i-propyl. In some embodiments, R is t-butyl. In someembodiments, R is SiMe₃. In some embodiments, R is SiPh₃.

In some embodiments, X₁ or X₂ is Ar, and Ar is Ar20. In someembodiments, D and D′ are the same, X₁ or X₂ is Ar, and Ar is Ar20. Insome embodiments, A is A1 or A3, D and D′ are the same, X₁ or X₂ is Ar,and Ar is Ar20.

In some embodiments the compound of Formula (I) or (II) is selected from

-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-dimethyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-dimethyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-dimethyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di-tert-butyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di-tert-butyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(pyridin-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(pyridin-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(pyridin-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-di(pyridin-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di(pyridin-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di(pyridin-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di(pyridin-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di(pyridin-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(pyridin-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(pyridin-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(pyridin-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di(pyridin-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-diphenyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-diphenyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-diphenyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-3-carbonitrile)    9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-phenyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-methyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(tert-butyl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-4-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-phenyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-methyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(tert-butyl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-4-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-phenyl-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-methyl-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(tert-butyl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-([1,1′-biphenyl]-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-3-yl)-9H-carbazole)-   9′,9″″-(5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(9′H-9,3′:6′,9″-tercarbazole)-   5,5′,5″,5′″-((5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[3,2-b]indole)-   4,4′,4″,4′″-((5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetraisophthalonitrile-   9,9′-(5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(3,6-di([1,1′-biphenyl]-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(3,6-di-p-tolyl-9H-carbazole)    3,3′,3″,3′″-((5-(2,6-diphenylpyridin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrabenzonitrile-   4,4′-((5-(2,6-diphenylpyridin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   5,5′-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(5H-pyrido[4,3-b]indole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(o-tolyl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-4-yl)-9H-carbazole)-   9,9′-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(9H-pyrido[3,4-b]indole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole)-   9′,9′″-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9-phenyl-9H,9′H-2,3′-bicarbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(6-phenylpyridin-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-fluoro-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(2,6-diphenylpyridin-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-4-yl)-9H-carbazole)    4,4′-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3-(p-tolyl)-9H-carbazole)-   9′,9″″-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9′H-9,3′:6′,9″-tercarbazole)-   5,5′,5″,5′″-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[4,3-b]indole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-di-o-tolyl-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-dimesityl-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-4-yl)-9H-carbazole)-   5,5′,5″,5′″-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[3,2-b]indole)-   9,9′,9″,9′″-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(9H-pyrido[2,3-b]indole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(2,6-dimethylphenyl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(3,5-dimethylphenyl)-9H-carbazole)-   9,9′,9″,9′″-((5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(9H-pyrido[3,4-b]indole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(6-phenylpyridin-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-difluoro-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(3,6-di-p-tolyl-9H-carbazole)-   9′,9″″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9′H-9,3′:6′,9″-tercarbazole)-   3,3′,3″,3′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrabenzonitrile-   5,5′,5″,5′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[4,3-b]indole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di-o-tolyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-dimesityl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-4-yl)-9H-carbazole)-   2,2′,2″,2′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetraisophthalonitrile-   5,5′,5″,5′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[3,2-b]indole)-   2,2′,2″,2′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrabenzonitrile-   9,9′,9″,9′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(9H-pyrido[2,3-b]indole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(2,6-dimethylphenyl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(3,5-dimethylphenyl)-9H-carbazole)-   9,9′,9″,9′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(9H-pyrido[3,4-b]indole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-difluoro-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-2-yl)-9H-carbazole)-   4,4′,4″,4′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetraisophthalonitrile-   5,5′,5″,5′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetraisophthalonitrile-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-2-yl)-9H-carbazole)-   4,4′,4″,4′″-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrabenzonitrile-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di-m-tolyl-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3,6-di-p-tolyl-9H-carbazole)-   9′,9″″-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9′H-9,3′:6′,9″-tercarbazole)-   5,5′,5″,5′″-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[4,3-b]indole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di-o-tolyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-dimesityl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-4-yl)-9H-carbazole)-   5,5′,5″,5′″-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(5H-pyrido[3,2-b]indole)-   9,9′,9″,9′″-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(9H-pyrido[2,3-b]indole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(2,6-dimethylphenyl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(3,5-dimethylphenyl)-9H-carbazole)-   9,9′,9″,9′″-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetrakis(9H-pyrido[3,4-b]indole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-4-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(6-phenylpyridin-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-difluoro-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-1-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-2-yl)-9H-carbazole)-   4,4′,4″,4′″-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3,6-triyl))tetraisophthalonitrile-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]furan-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-bis(dibenzo[b,d]thiophen-1-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di-m-tolyl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3,6-di-p-tolyl-9H-carbazole)-   9′,9′″-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9-phenyl-9H,9′H-3,3′-bicarbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(o-tolyl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-mesityl-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-4-yl)-9H-carbazole)-   5,5′-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(5H-pyrido[3,2-b]indole)-   9,9′-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(9H-pyrido[2,3-b]indole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(2,6-dimethylphenyl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(3,5-dimethylphenyl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole)-   9′,9′″-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9-phenyl-9H,9′H-2,3′-bicarbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-1-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(6-phenylpyridin-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-3-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-fluoro-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(2,6-diphenylpyridin-4-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-1-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-4-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole)-   4,4′-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   5,5′-((5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-2-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-1-yl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(m-tolyl)-9H-carbazole)-   9,9′-(5-(2,6-diphenylpyrimidin-4-yl)-1,3-phenylene)bis(3-(p-tolyl)-9H-carbazole)    4,4′-((5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   9,9′-(5-(4,6-diphenylpyridin-2-yl)-1,3-phenylene)bis(3-(p-tolyl)-9H-carbazole)-   3,3′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))dibenzonitrile-   5,5′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(5H-pyrido[4,3-b]indole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(o-tolyl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-mesityl-9H-carbazole)-   2,2′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   5,5′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(5H-pyrido[3,2-b]indole)-   2,2′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))dibenzonitrile-   9,9′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(9H-pyrido[2,3-b]indole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(2,6-dimethylphenyl)-9H-carbazole)-   9,9″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9′-phenyl-9H,9′H-3,4′-bicarbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(3,5-dimethylphenyl)-9H-carbazole)-   9,9′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))bis(9H-pyrido[3,4-b]indole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(trifluoromethyl)-9H-carbazole)-   9′,9′″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9-phenyl-9H,9′H-2,3′-bicarbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-1-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(6-phenylpyridin-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-3-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-fluoro-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(2,6-diphenylpyridin-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-2-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(9,9′-spirobi[fluoren]-4-yl)-9H-carbazole)-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]thiophen-2-yl)-9H-carbazole)-   9′,9′″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9-phenyl-9H,9′H-1,3′-bicarbazole)-   4,4′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   5,5′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))diisophthalonitrile-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(dibenzo[b,d]furan-2-yl)-9H-carbazole)-   4,4′-((5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole-9,3-diyl))dibenzonitrile-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(m-tolyl)-9H-carbazole);    and-   9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(3-(p-tolyl)-9H-carbazole).

In some embodiments, the compound of Formula (I) or (II) is selectedfrom:

In some embodiments, the compound of Formula (I) or (II) is selectedfrom

In some embodiments, compounds of Formula (I) or (II) are substitutedwith deuterium.

In some embodiments, compounds of Formula (I) or (II) are light-emittingmaterials.

In some embodiments, compounds of Formula (I) or (II) are compoundcapable of emitting delayed fluorescence.

In some embodiments of the present disclosure, when excited via thermalor electronic means, the compounds of Formula (I) or (II) can producelight in ultraviolet region, the blue, green, yellow, orange, or redregion of the visible spectrum (e.g., about 420 nm to about 500 nm,about 500 nm to about 600 nm, or about 600 nm to about 700 nm), ornear-infrared region.

In some embodiments of the present disclosure, when excited via thermalor electronic means, the compounds of Formula (I) or (II) can producelight in the red or orange region of the visible spectrum (e.g., about620 nm to about 780 nm; about 650 nm).

In some embodiments of the present disclosure, when excited via thermalor electronic means, the compounds of Formula (I) or (II) can producelight in the orange or yellow region of the visible spectrum (e.g.,about 570 nm to about 620 nm; about 590 nm; about 570 nm).

In some embodiments of the present disclosure, when excited via thermalor electronic means, the compounds of Formula (I) or (II) can producelight in the green region of the visible spectrum (e.g., about 490 nm toabout 575 nm; about 510 nm).

In some embodiments of the present disclosure, when excited via thermalor electronic means, the compounds of Formula (I) or (II) can producelight in the blue region of the visible spectrum (e.g., about 400 nm toabout 490 nm; about 475 nm).

Electronic properties of a library of small chemical molecules can becomputed using known ab initio quantum mechanical computations. Forexample, using a time-dependent density functional theory using, as abasis set, the set of functions known as 6-31G* and a Becke,3-parameter, Lee-Yang-Parr hybrid functional to solve Hartree-Fockequations (TD-DFT/B3LYP/6-31G*), molecular fragments (moieties) can bescreened which have HOMOs above a specific threshold and LUMOs below aspecific threshold, and wherein the calculated triplet state of themoieties is above 2.75 eV.

Therefore, for example, a donor moiety (“D”) can be selected because ithas a HOMO energy (e.g., an ionization potential) of greater than orequal to −6.5 eV. An acceptor moiety (“A”) can be selected because ithas, for example, a LUMO energy (e.g., an electron affinity) of lessthan or equal to −0.5 eV. The linker moiety (“L”) can be a rigidconjugated system which can, for example, sterically restrict theacceptor and donor moieties into a specific configuration, therebypreventing the overlap between the conjugated a system of donor andacceptor moieties.

In some embodiments, the compound library is filtered using one or moreof the following properties:

-   -   1. emission near a certain wavelength;    -   2. calculated triplet state above a certain energy level;    -   3. ΔE_(ST) value below a certain value;    -   4. quantum yield above a certain value;    -   5. HOMO level; and    -   6. LUMO level.

In some embodiments, the difference between the lowest singlet excitedstate and the lowest triplet excited state at 77K (ΔE_(ST)) is less thanabout 0.5 eV, less than about 0.4 eV, less than about 0.3 eV, less thanabout 0.2 eV, or less than about 0.1 eV. In some embodiments, theΔE_(ST) value is less than about 0.09 eV, less than about 0.08 eV, lessthan about 0.07 eV, less than about 0.06 eV, less than about 0.05 eV,less than about 0.04 eV, less than about 0.03 eV, less than about 0.02eV, or less than about 0.01 eV.

In some embodiments, a compound of Formula (I) or (II) exhibits aquantum yield of greater than 25%, such as about 30%, about 35%, about40%, about 45%, about 50%, about 55%, about 60%/a, about 65%, about 70%,about 75%, about 80%, about 85%, about 90%, about 95%, or greater.

Compositions with the Disclosed Compounds

In some embodiments, a compound of Formula (I) or (II) is combined with,dispersed within, covalently bonded to, coated with, formed on, orotherwise associated with, one or more materials (e.g., small molecules,polymers, metals, metal complexes, etc.) to form a film or layer insolid state. For example, the compound of Formula (I) or (II) may becombined with an electroactive material to form a film. In some cases,the compound of Formula (I) or (II) may be combined with ahole-transport polymer. In some cases, the compound of Formula (I) or(II) may be combined with an electron-transport polymer. In some cases,the compound of Formula (I) or (II) may be combined with ahole-transport polymer and an electron-transport polymer. In some cases,the compound of Formula (I) or (II) may be combined with a copolymercomprising both hole-transport portions and electron-transport portions.In such embodiments, electrons and/or holes formed within the solid filmor layer may interact with the compound of Formula (I) or (II).

Exemplary Uses of the Disclosed Compound

Organic Light-Emitting Diodes

One aspect of the invention relates to use of the compound of Formula(I) or (II) of the invention as a light-emitting material of an organiclight-emitting device. In some embodiments, the compound represented bythe Formula (I) or (II) of the invention may be effectively used as alight-emitting material in a light-emitting layer of an organiclight-emitting device. In some embodiments, the compound of Formula (I)or (II) comprises a delayed fluorescent material emitting delayedfluorescent light (delayed fluorescence emitter).

In some embodiments, the invention provides a delayed fluorescenceemitter having the structure of Formula (I) or (II). In someembodiments, the invention relates to the use of the compound of Formula(I) or (II) as the delayed fluorescence emitter. In some embodiments,the light-emitting layer comprises a compound of Formula (I) or (II) asan assist dopant. In some embodiments, the compound of Formula (I) or(II) can be used as a host material and used with one or morelight-emitting materials, and the light-emitting material can be afluorescent material, a phosphorescent material or a TADF material. Insome embodiments, the compound of Formula (I) or (II) can be used as ahole transport material. In some embodiments, the compound of Formula(I) or (II) can be used as an electron transport material. In someembodiments, the invention relates to a method for emitting delayedfluorescent light from the compound of Formula (I) or (II). In someembodiments, an organic light-emitting device comprising the compound asa light-emitting material, emits delayed fluorescent light, and has ahigh light emission efficiency.

In some embodiments, a light-emitting layer comprises a compound ofFormula (I) or (II), wherein the compound of Formula (I) or (II) isoriented parallel to the substrate. In some embodiments, the substrateis a film forming surface. In some embodiments, the orientation of thecompound of Formula (I) or (II) with respect to the film forming surfaceinfluences or determines the propagation directions of the light emittedby the compound to be aligned. In some embodiments, the alignment of thepropagation directions of the light emitted by the compound of Formula(I) or (II) enhances the light extraction efficiency from thelight-emitting layer.

One aspect of the invention relates to an organic light-emitting device.In some embodiments, the organic light-emitting device comprises alight-emitting layer. In some embodiments, the light-emitting layercomprises a compound of Formula (I) or (II) as a light-emittingmaterial. In some embodiments, the organic light-emitting device is anorganic photoluminescent device (organic PL device). In someembodiments, the organic light-emitting device is an organicelectroluminescent device (organic EL device). In some embodiments, thecompound of Formula (I) or (II) assists the light emission of anotherlight-emitting material comprised in the light-emitting layer, i.e., asa so-called assistant dopant. In some embodiments, the compound ofFormula (I) or (II) comprised in the light-emitting layer is in its thelowest excited singlet energy level, which is comprised between thelowest excited singlet energy level of the host material comprised inthe light-emitting layer and the lowest excited singlet energy level ofanother light-emitting material comprised in the light-emitting layer.

In some embodiments, the organic photoluminescent device comprises atleast one light-emitting layer. In some embodiments, the organicelectroluminescent device comprises at least an anode, a cathode, and anorganic layer between the anode and the cathode. In some embodiments,the organic layer comprises at least a light-emitting layer. In someembodiments, the organic layer comprises only a light-emitting layer. Insome embodiments, the organic layer, comprises one or more organiclayers in addition to the light-emitting layer. Examples of the organiclayer include a hole transporting layer, a hole injection layer, anelectron barrier layer, a hole barrier layer, an electron injectionlayer, an electron transporting layer and an exciton barrier layer. Insome embodiments, the hole transporting layer may be a hole injectionand transporting layer having a hole injection function, and theelectron transporting layer may be an electron injection andtransporting layer having an electron injection function. An example ofan organic electroluminescent device is shown in the FIGURE.

Substrate

In some embodiments, the organic electroluminescent device of theinvention is supported by a substrate, wherein the substrate is notparticularly limited and may be any of those that have been commonlyused in an organic electroluminescent device, for example those formedof glass, transparent plastics, quartz and silicon.

Anode

In some embodiments, the anode of the organic electroluminescent deviceis made of a metal, an alloy, an electroconductive compound, or acombination thereof. In some embodiments, the metal, alloy, orelectroconductive compound has a large work function (4 eV or more). Insome embodiments, the metal is Au. In some embodiments, theelectroconductive transparent material is selected from CuI, indium tinoxide (ITO), SnO₂, and ZnO. In some embodiments, an amorphous materialcapable of forming a transparent electroconductive film, such as IDIXO(In₂O₃—ZnO), is be used. In some embodiments, the anode is a thin film.In some embodiments the thin film is made by vapor deposition orsputtering. In some embodiments, the film is patterned by aphotolithography method. In some embodiments, where the pattern may notrequire high accuracy (for example, approximately 100 μm or more), thepattern may be formed with a mask having a desired shape on vapordeposition or sputtering of the electrode material. In some embodiments,when a material can be applied as a coating, such as an organicelectroconductive compound, a wet film forming method, such as aprinting method and a coating method is used. In some embodiments, whenthe emitted light goes through the anode, the anode has a transmittanceof more than 10%, and the anode has a sheet resistance of severalhundred Ohm per square or less. In some embodiments, the thickness ofthe anode is from 10 to 1,000 nm. In some embodiments, the thickness ofthe anode is from 10 to 200 nm. In some embodiments, the thickness ofthe anode varies depending on the material used.

Cathode

In some embodiments, the cathode is made of an electrode material ametal having a small work function (4 eV or less) (referred to as anelectron injection metal), an alloy, an electroconductive compound, or acombination thereof. In some embodiments, the electrode material isselected from sodium, a sodium-potassium alloy, magnesium, lithium, amagnesium-cupper mixture, a magnesium-silver mixture, amagnesium-aluminum mixture, a magnesium-indium mixture, analuminum-aluminum oxide (Al₂O₃) mixture, indium, a lithium-aluminummixture, and a rare earth metal. In some embodiments, a mixture of anelectron injection metal and a second metal that is a stable metalhaving a larger work function than the electron injection metal is used.In some embodiments, the mixture is selected from a magnesium-silvermixture, a magnesium-aluminum mixture, a magnesium-indium mixture, analuminum-aluminum oxide (Al₂O₃) mixture, a lithium-aluminum mixture, andaluminium. In some embodiments, the mixture increases the electroninjection property and the durability against oxidation. In someembodiments, the cathode is produced by forming the electrode materialinto a thin film by vapor deposition or sputtering. In some embodiments,the cathode has a sheet resistance of several hundred Ohm per square orless. In some embodiments, the thickness of the cathode ranges from 10nm to 5 μm. In some embodiments, the thickness of the cathode rangesfrom 50 to 200 nm. In some embodiments, for transmitting the emittedlight, any one of the anode and the cathode of the organicelectroluminescent device is transparent or translucent. In someembodiments, the transparent or translucent electroluminescent devicesenhances the light emission luminance.

In some embodiments, the cathode is formed with an electroconductivetransparent material, as described for the anode, to form a transparentor translucent cathode. In some embodiments, a device comprises an anodeand a cathode, both being transparent or translucent.

Light-Emitting Layer

In some embodiments, the light-emitting layer is a layer, in which holesand electrons, injected respectively from the anode and the cathode, arerecombined to form excitons. In some embodiments the layer emits light.

In some embodiments, a light-emitting material is solely used as thelight-emitting layer. In some embodiments, the light-emitting layercontains a light-emitting material, and a host material. In someembodiments, the light-emitting material is one or more compounds ofFormula (I) or (II). In some embodiments, for the organicelectroluminescent device and the organic photoluminescent device toexhibit a high light emission efficiency, the singlet excitons and thetriplet excitons generated in the light-emitting material are confinedin the light-emitting material. In some embodiments, a host material isused in addition to the light-emitting material in the light-emittinglayer. In some embodiments, the host material is an organic compound. Insome embodiments, the organic compounds have excited singlet energy andexcited triplet energy, at least one of which is higher than those ofthe light-emitting material of the invention. In some embodiments, thesinglet excitons and the triplet excitons generated in thelight-emitting material of the invention are confined in the moleculesof the light-emitting material of the invention. In some embodiments,the singlet and triplet excitons are sufficiently confined to elicit thelight emission efficiency. In some embodiments, the singlet excitons andthe triplet excitons are not confined sufficiently, though a high lightemission efficiency is still obtained, and thus a host material capableof achieving a high light emission efficiency can be used in theinvention without any particular limitation. In some embodiments, thelight emission occurs in the light-emitting material of thelight-emitting layer in the devices of the invention. In someembodiments, the emitted light contains both fluorescent light anddelayed fluorescent light. In some embodiments, the emitted lightcomprises emitted light from the host material. In some embodiments, theemitted light consists of emitted light from the host material. In someembodiments, the emitted light comprises emitted light from a compoundof Formula (I) or (II), and emitted light from the host material. Insome embodiments, a TADF molecule and a host material are used. In someembodiments, the TADF is an assistant dopant.

In some embodiments, when a host material is used, the amount of thecompound of the invention as the light-emitting material contained inthe light-emitting layer is 0.1% by weight or more. In some embodiments,when a host material is used, the amount of the compound of theinvention as the light-emitting material contained in the light-emittinglayer is 1% by weight or more. In some embodiments, when a host materialis used, the amount of the compound of the invention as thelight-emitting material contained in the light-emitting layer is 50% byweight or less. In some embodiments, when a host material is used, theamount of the compound of the invention as the light-emitting materialcontained in the light-emitting layer is 20% by weight or less. In someembodiments, when a host material is used, the amount of the compound ofthe invention as the light-emitting material contained in thelight-emitting layer is 10% by weight or less.

In some embodiments, the host material in the light-emitting layer is anorganic compound comprising a hole transporting function and an electrontransporting function. In some embodiments, the host material in thelight-emitting layer is an organic compound that prevents the emittedlight from being increased in wavelength. In some embodiments, the hostmaterial in the light-emitting layer is an organic compound with a highglass transition temperature.

In some embodiments, the host material is selected from the groupconsisting of:

Injection Layer

An injection layer is a layer between the electrode and the organiclayer. In some embodiments, the injection layer decreases the drivingvoltage and enhances the light emission luminance. In some embodiments,the injection layer includes a hole injection layer and an electroninjection layer. The injection layer can be positioned between the anodeand the light-emitting layer or the hole transporting layer, and betweenthe cathode and the light-emitting layer or the electron transportinglayer. In some embodiments, an injection layer is present. In someembodiments, no injection layer is present.

Barrier Layer

A barrier layer is a layer capable of inhibiting charges (electrons orholes) and/or excitons present in the light-emitting layer from beingdiffused outside the light-emitting layer. In some embodiments, theelectron barrier layer is between the light-emitting layer and the holetransporting layer, and inhibits electrons from passing through thelight-emitting layer toward the hole transporting layer. In someembodiments, the hole barrier layer is between the light-emitting layerand the electron transporting layer, and inhibits holes from passingthrough the light-emitting layer toward the electron transporting layer.In some embodiments, the barrier layer inhibits excitons from beingdiffused outside the light-emitting layer. In some embodiments, theelectron barrier layer and the hole barrier layer are exciton barrierlayers. As used herein, the term “electron barrier layer” or “excitonbarrier layer” includes a layer that has the functions of both electronbarrier layer and of an exciton barrier layer.

Hole Barrier Layer

A hole barrier layer acts as an electron transporting layer. In someembodiments, the hole barrier layer inhibits holes from reaching theelectron transporting layer while transporting electrons. In someembodiments, the hole barrier layer enhances the recombinationprobability of electrons and holes in the light-emitting layer. Thematerial for the hole barrier layer may be the same materials as theones described for the electron transporting layer.

Electron Barrier Layer

As electron barrier layer transports holes. In some embodiments, theelectron barrier layer inhibits electrons from reaching the holetransporting layer while transporting holes. In some embodiments, theelectron barrier layer enhances the recombination probability ofelectrons and holes in the light-emitting layer. Next, preferredexamples of compounds usable as an electron barrier material arementioned below.

Exciton Barrier Layer

An exciton barrier layer inhibits excitons generated throughrecombination of holes and electrons in the light-emitting layer frombeing diffused to the charge transporting layer. In some embodiments,the exciton barrier layer enables effective confinement of excitons inthe light-emitting layer. In some embodiments, the light emissionefficiency of the device is enhanced. In some embodiments, the excitonbarrier layer is adjacent to the light-emitting layer on any of the sideof the anode and the side of the cathode, and on both the sides. In someembodiments, where the exciton barrier layer is on the side of theanode, the layer can be between the hole transporting layer and thelight-emitting layer and adjacent to the light-emitting layer. In someembodiments, where the exciton barrier layer is on the side of thecathode, the layer can be between the light-emitting layer and thecathode and adjacent to the light-emitting layer. In some embodiments, ahole injection layer, an electron barrier layer, or a similar layer isbetween the anode and the exciton barrier layer that is adjacent to thelight-emitting layer on the side of the anode. In some embodiments, ahole injection layer, an electron barrier layer, a hole barrier layer,or a similar layer is between the cathode and the exciton barrier layerthat is adjacent to the light-emitting layer on the side of the cathode.In some embodiments, the exciton barrier layer comprises excited singletenergy and excited triplet energy, at least one of which is higher thanthe excited singlet energy and the excited triplet energy of thelight-emitting material, respectively.

Hole Transporting Layer

The hole transporting layer comprises a hole transporting material. Insome embodiments, the hole transporting layer is a single layer. In someembodiments, the hole transporting layer comprises a plurality oflayers.

In some embodiments, the hole transporting material has one of injectionor transporting property of holes and barrier property of electrons. Insome embodiments, the hole transporting material is an organic material.In some embodiments, the hole transporting material is an inorganicmaterial. Examples of known hole transporting materials that may be usedherein include but are not limited to a triazole derivative, anoxadiazole derivative, an imidazole derivative, a carbazole derivative,an indolocarbazole derivative, a polyarylalkane derivative, a pyrazolinederivative, a pyrazolone derivative, a phenylenediamine derivative, anarylamine derivative, an amino-substituted chalcone derivative, anoxazole derivative, a styrylanthracene derivative, a fluorenonederivative, a hydrazone derivative, a stilbene derivative, a silazanederivative, an aniline copolymer and an electroconductive polymeroligomer, particularly a thiophene oligomer, or a combination thereof.In some embodiments, the hole transporting material is selected from aporphyrin compound, an aromatic tertiary amine compound, and astyrylamine compound. In some embodiments, the hole transportingmaterial is an aromatic tertiary amine compound. Next, preferredexamples of compounds usable as a hole transport material are mentionedbelow.

Electron Transporting Layer

The electron transporting layer comprises an electron transportingmaterial. In some embodiments, the electron transporting layer is asingle layer. In some embodiments, the electron transporting layercomprises a plurality of layer.

In some embodiments, the electron transporting material needs only tohave a function of transporting electrons, which are injected from thecathode, to the light-emitting layer. In some embodiments, the electrontransporting material also function as a hole barrier material. Examplesof the electron transporting layer that may be used herein include butare not limited to a nitro-substituted fluorene derivative, adiphenylquinone derivative, a thiopyran dioxide derivative,carbodiimide, a fluorenylidene methane derivative, anthraquinodimethane,an anthrone derivatives, an oxadiazole derivative, an azole derivative,an azine derivative, or a combination thereof, or a polymer thereof. Insome embodiments, the electron transporting material is a thiadiazolederivative, or a quinoxaline derivative. In some embodiments, theelectron transporting material is a polymer material. Next, preferredexamples of compounds usable as an electron transport material arementioned below.

Molecular Weight

The molecular weight of the compound represented by the Formula (I) or(II) is, for example, in the case of using it by forming an organiclayer that contains a compound represented by the Formula (I) or (II)according to a vapor deposition method, preferably 1500 or less, morepreferably 1200 or less, even more preferably 1000 or less, still morepreferably 900 or less.

Polymer

Compounds of Formula (I) or (II) may be formed into a film according toa coating method irrespective of the molecular weight of the compound.Accordingly, even a compound having a relatively large molecular weightcan be formed into a film.

In some embodiments, a film comprises a plurality of independentlyselected compounds of Formula (I) or (II). In some embodiments, acompound of Formula (I) or (II) is modified to incorporate apolymerizable group. The modified compound is then polymerized to obtaina polymer comprising a compound of Formula (I) or (II). For example, amonomer is obtained by replacing any one of the hydrogen of a compoundof Formula (I) or (II) by a polymerizable functional group. The monomeris then homo-polymerized or copolymerized with any other monomer to givea polymer having a repeating unit. Alternatively, different compounds ofFormula (I) or (II) are coupled to give a dimer or a trimer. Examples ofthe polymer having a repeating unit comprising a compound of Formula (I)or (II) include polymers comprising a unit of Formula (A) or (B).

wherein:

Q represents a group containing a compound of Formula (I) or (II);

L¹ and L² each represents a linking group; and

R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ each independently represent a substituent.

In some embodiments, the linking group is preferably 0 to 20 carbons,more preferably 1 to 15, even more preferably 2 to 10. In someembodiments, the linking is —X¹¹-L¹¹-; wherein X¹¹ is oxygen or sulphur,and L¹¹ represents a linking group.

In some embodiments, X¹¹ is oxygen. In some embodiments, L¹¹ is asubstituted or unsubstituted alkylene or a substituted or unsubstitutedarylene. In some embodiments, the substituted or unsubstituted alkyleneis C1 to C10 alkylene. In some embodiments, substituted or unsubstitutedarylene is substituted or unsubstituted phenylene.

In some embodiments, R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ are independently asubstituted or unsubstituted alkyl group having 1 to 6 carbon atoms, asubstituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, ora halogen atom. In some embodiments, R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ areindependently unsubstituted alkyl having 1 to 3 carbon atoms, anunsubstituted alkoxy having 1 to 3 carbon atoms, a fluorine atom or achlorine atom. In some embodiments, R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ areindependently unsubstituted alkyl group having 1 to 3 carbon atoms, oran unsubstituted alkoxy 5 group having 1 to 3 carbon atoms.

L¹ and L² may be introduced by replacing any one of the hydrogen in thestructure of the Formula (I) or (II). Two or more linking groups maybond to one Q to form a crosslinked structure or a network structure.

Specific structural examples of the repeating unit include structuresrepresented by the following Formulae (C) to (F).

Polymers having a repeating unit of the Formulae (C) to (F) may besynthesized by replacing any one of the hydrogen by a hydroxy group intoa structure of the Formula (I) or (II), then introducing a polymerizablegroup into the structure through reaction with any of the followingcompounds via the hydroxy group serving as a linker, and polymerizingthe polymerizable group.

The polymer having a structure represented by the Formula (I) or (II)may be a polymer containing a repeating unit alone having a structurerepresented by the Formula (I) or (II) or may be a polymer containing arepeating unit having any other structure. The repeating unit having astructure represented by the Formula (I) or (II) contained in thepolymer may be one type alone or may contain two or more types ofrepeating units. A repeating unit not having a structure represented bythe Formula (I) or (II) includes those derived from monomers to be usedin ordinary copolymerization. For example, there are mentioned repeatingunits derived from monomers having an ethylenic unsaturated bond such asethylene, styrene, etc.

In some embodiments, a compound of Formula (I) or (II) is comprised inthe light-emitting layer of a device of the invention. In someembodiments, a compound of Formula (I) or (II) is comprised in thelight-emitting layer and at least one other layers. In some embodiments,the compounds of Formula (I) or (II) are independently selected for eachlayers. In some embodiments, the compounds of Formula (I) or (II) arethe same. In some embodiments, the compounds of Formula (I) or (II) aredifferent. For example, the compound represented by the Formula (I) or(II) may be used in the injection layer, the barrier layer, the holebarrier layer, the electron barrier layer, the exciton barrier layer,the hole transporting layer, the electron transporting layer and thelike described above. The film forming method of the layers are notparticularly limited, and the layers may be produced by any dryprocesses and/or wet processes.

Specific examples of materials that can be used in the organicelectroluminescent device are shown above, but the materials that may beused in the invention are not construed as being limited to the examplecompounds. In some embodiments, a material having a particular functioncan also have another function.

Film Forming Method

The compound of the invention may be formed as a film on a substrate byany methods.

Before forming the film, the substrate may be heated or cooled, and thefilm quality and the molecular packing in the film may be controlled bychanging the temperature of the substrate. The temperature of thesubstrate is not particularly limited, and is preferably in a range of 0to 200° C., more preferably in a range of 15 to 100° C., andparticularly preferably in a range of 20 to 95° C.

Before forming a film of the compound of the invention on a substrate,the film may be formed by a vacuum process or a solution process, bothof which are preferred.

Specific examples of the film formation by a vacuum process include aphysical vapor deposition, such as vacuum deposition, sputtering method,ion plating method and molecular beam epitaxy (MBE), and chemical vapordeposition (CVD), such as plasma polymerization, and vacuum depositionis preferably used.

The film formation by a solution process means a method, in which anorganic compound is dissolved in a solvent capable of dissolving thesame, and a film is formed by using the resulting solution. Specificexamples thereof include ordinary methods, for example, a coatingmethod, such as a casting method, a dip coating method, a die coatermethod, a roll coater method, a bar coater method and a spin coatingmethod, a printing method, such as ink-jet method, screen printingmethod, gravure printing method, flexography printing method, offsetprinting method and microcontact printing method, and Langmuir-Blodgett(LB) method, and casting method, spin-coating method, preferably ink-jetmethod, gravure printing method, flexography printing method, offsetprinting method and microcontact printing method are used.

The coating solution for an organic semiconductor device of theinvention capable of being used for film formation by a solution processwill be described below.

In the case where the film is formed on a substrate by a solutionprocess, the material for forming the layer may be dissolved ordispersed in a suitable organic solvent (for example, a hydrocarbonsolvent, such as hexane, octane, decane, toluene, xylene, mesitylene,ethylbenzene, decalin and 1-methylnaphthalene, a ketone solvent, such asacetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone,a halogenated hydrocarbon solvent, such as dichloromethane, chloroform,tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane,chlorobenzene, dichlorobenzene and chlorotoluene, an ester solvent, suchas ethyl acetate, butyl acetate and amyl acetate, an alcohol solvent,such as methanol, ethanol, propanol, butanol, pentanol, hexanol,cyclohexanol, methyl cellosolve, ethyl cellosolve and ethylene glycol,an ether solvent, such as diethyl ether, dibutyl ether, tetrahydrofuran,dioxane and anisole, an amide or imide solvent, such asN,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone and1-methyl-2-imidazolidinone, a sulfoxide solvent, such asdimethylsulfoxide, and a nitrile solvent, such as acetonitrile) and/orwater to prepare a coating liquid, which may be then coated by variouscoating methods to form the thin film.

Devices

In some embodiments, the compounds of the disclosure are incorporatedinto a device. For example, the device includes, but is not limited toan OLED bulb, an OLED lamp, a television screen, a computer monitor, amobile phone, and a tablet.

In some embodiments, an electronic device comprises an OLED comprisingan anode, a cathode, and at least one organic layer comprising alight-emitting layer between the anode and the cathode, wherein thelight-emitting layer comprises

a host material; and

a compound of Formula (I) or (II).

In some embodiments, the light-emitting layer comprises a compound ofFormula (I) or (II) as a light-emitting material.

In some embodiments, the light-emitting layer comprises a compound ofFormula (I) or (II) as an assist dopant.

In some embodiments, the light-emitting layer of the OLED furthercomprises a fluorescent material wherein the compound of Formula (I) or(II) converts triplets to singlets for the fluorescent emitter.

In some embodiments, compositions described herein may be incorporatedinto various light-sensitive or light-activated devices, such as a OLEDsor photovoltaic devices. In some embodiments, the composition may beuseful in facilitating charge transfer or energy transfer within adevice and/or as a hole-transport material. The device may be, forexample, an organic light-emitting diode (OLED), an organic integratedcircuit (O-IC), an organic field-effect transistor (O-FET), an organicthin-film transistor (O-TFT), an organic light-emitting transistor(O-LET), an organic solar cell (O-SC), an organic optical detector, anorganic photoreceptor, an organic field-quench device (O-FQD), alight-emitting electrochemical cell (LEC) or an organic laser diode(O-laser).

Bulbs or Lamps

In some embodiments, an electronic device comprises an OLED comprisingan anode, a cathode, and at least one organic layer comprising alight-emitting layer between the anode and the cathode, wherein thelight-emitting layer comprises

a host material;

a compound of Formula (I) or (II); wherein the compound of Formula (I)or (II) is a light-emitting material; and

an OLED driver circuit.

In some embodiments, the light-emitting layer comprises a compound ofFormula (I) or (II) as an assist dopant.

In some embodiments, a device comprises OLEDs that differ in color. Insome embodiments, a device comprises an array comprising a combinationof OLEDs. In some embodiments, the combination of OLEDs is a combinationof three colors (e.g., RGB). In some embodiments, the combination ofOLEDs is a combination of colors that are not red, green, or blue (forexample, orange and yellow green). In some embodiments, the combinationof OLEDs is a combination of two, four, or more colors.

In some embodiments, a device is an OLED light comprising:

a circuit board having a first side with a mounting surface and anopposing second side, and defining at least one aperture;

at least one OLED on the mounting surface, the at least one OLEDconfigured to emanate light, comprising:

-   -   an anode, a cathode, and at least one organic layer comprising a        light-emitting layer between the anode and the cathode, wherein        the light-emitting layer comprises    -   a host material;    -   a compound of Formula (I) or (II); wherein the compound of        Formula (I) or (II) is a light-emitting material;

a housing for the circuit board; and

at least one connector arranged at an end of the housing, the housingand the connector defining a package adapted for installation in a lightfixture.

In some embodiments, the light-emitting layer comprises a compound ofFormula (I) or (II) as an assist dopant.

In some embodiments, the OLED light comprises a plurality of OLEDsmounted on a circuit board such that light emanates in a plurality ofdirections. In some embodiments, a portion of the light emanated in afirst direction is deflected to emanate in a second direction. In someembodiments, a reflector is used to deflect the light emanated in afirst direction.

Displays or Screens

In some embodiments, the compounds of Formula (I) or (II) can be used ina screen or a display. In some embodiments, the compounds of Formula (I)or (II) are deposited onto a substrate using a process including, butnot limited to, vacuum evaporation, deposition, vapor deposition, orchemical vapor deposition (CVD). In some embodiments, the substrate is aphotoplate structure useful in a two-sided etch provides a unique aspectratio pixel. The screen (which may also be referred to as a mask) isused in a process in the manufacturing of OLED displays. Thecorresponding artwork pattern design facilitates a very steep and narrowtie-bar between the pixels in the vertical direction and a large,sweeping bevel opening in the horizontal direction. This allows theclose patterning of pixels needed for high definition displays whileoptimizing the chemical deposition onto a TFT backplane.

The internal patterning of the pixel allows the construction of a3-dimensional pixel opening with varying aspect ratios in the horizontaland vertical directions. Additionally, the use of imaged “stripes” orhalftone circles within the pixel area inhibits etching in specificareas until these specific patterns are undercut and fall off thesubstrate. At that point the entire pixel area is subjected to a similaretch rate but the depths are varying depending on the halftone pattern.Varying the size and spacing of the halftone pattern allows etching tobe inhibited at different rates within the pixel allowing for alocalized deeper etch needed to create steep vertical bevels.

A preferred material for the deposition mask is invar. Invar is a metalalloy that is cold rolled into long thin sheet in a steel mill. Invarcannot be electrodeposited onto a rotating mandrel as the nickel mask. Apreferred and more cost feasible method for forming the open areas inthe mask used for deposition is through a wet chemical etching.

In some embodiments, a screen or display pattern is a pixel matrix on asubstrate. In some embodiments, a screen or display pattern isfabricated using lithography (e.g., photolithography and e-beamlithography). In some embodiments, a screen or display pattern isfabricated using a wet chemical etch. In further embodiments, a screenor display pattern is fabricated using plasma etching.

Methods of Manufacturing Devices Using the Disclosed Compounds

An OLED display is generally manufactured by forming a large motherpanel and then cutting the mother panel in units of cell panels. Ingeneral, each of the cell panels on the mother panel is formed byforming a thin film transistor (TFT) including an active layer and asource/drain electrode on a base substrate, applying a planarizationfilm to the TFT, and sequentially forming a pixel electrode, alight-emitting layer, a counter electrode, and an encapsulation layer,and then is cut from the mother panel.

An OLED display is generally manufactured by forming a large motherpanel and then cutting the mother panel in units of cell panels. Ingeneral, each of the cell panels on the mother panel is formed byforming a thin film transistor (TFT) including an active layer and asource/drain electrode on a base substrate, applying a planarizationfilm to the TFT, and sequentially forming a pixel electrode, alight-emitting layer, a counter electrode, and an encapsulation layer,and then is cut from the mother panel.

In another aspect, provided herein is a method of manufacturing anorganic light-emitting diode (OLED) display, the method comprising:

forming a barrier layer on a base substrate of a mother panel;

forming a plurality of display units in units of cell panels on thebarrier layer;

forming an encapsulation layer on each of the display units of the cellpanels;

applying an organic film to an interface portion between the cellpanels.

In some embodiments, the barrier layer is an inorganic film formed of,for example, SiNx, and an edge portion of the barrier layer is coveredwith an organic film formed of polyimide or acryl. In some embodiments,the organic film helps the mother panel to be softly cut in units of thecell panel.

In some embodiments, the thin film transistor (TFT) layer includes alight-emitting layer, a gate electrode, and a source/drain electrode.Each of the plurality of display units may include a thin filmtransistor (TFT) layer, a planarization film formed on the TFT layer,and a light-emitting unit formed on the planarization film, wherein theorganic film applied to the interface portion is formed of a samematerial as a material of the planarization film and is formed at a sametime as the planarization film is formed. In some embodiments, alight-emitting unit is connected to the TFT layer with a passivationlayer and a planarization film therebetween and an encapsulation layerthat covers and protects the light-emitting unit. In some embodiments ofthe method of manufacturing, the organic film contacts neither thedisplay units nor the encapsulation layer.

Each of the organic film and the planarization film may include any oneof polyimide and acryl. In some embodiments, the barrier layer may be aninorganic film. In some embodiments, the base substrate may be formed ofpolyimide. The method may further include, before the forming of thebarrier layer on one surface of the base substrate formed of polyimide,attaching a carrier substrate formed of a glass material to anothersurface of the base substrate, and before the cutting along theinterface portion, separating the carrier substrate from the basesubstrate. In some embodiments, the OLED display is a flexible display.

In some embodiments, the passivation layer is an organic film disposedon the TFT layer to cover the TFT layer. In some embodiments, theplanarization film is an organic film formed on the passivation layer.In some embodiments, the planarization film is formed of polyimide oracryl, like the organic film formed on the edge portion of the barrierlayer. In some embodiments, the planarization film and the organic filmare simultaneously formed when the OLED display is manufactured. In someembodiments, the organic film may be formed on the edge portion of thebarrier layer such that a portion of the organic film directly contactsthe base substrate and a remaining portion of the organic film contactsthe barrier layer while surrounding the edge portion of the barrierlayer.

In some embodiments, the light-emitting layer includes a pixelelectrode, a counter electrode, and an organic light-emitting layerdisposed between the pixel electrode and the counter electrode. In someembodiments, the pixel electrode is connected to the source/drainelectrode of the TFT layer.

In some embodiments, when a voltage is applied to the pixel electrodethrough the TFT layer, an appropriate voltage is formed between thepixel electrode and the counter electrode, and thus the organiclight-emitting layer emits light, thereby forming an image. Hereinafter,an image forming unit including the TFT layer and the light-emittingunit is referred to as a display unit.

In some embodiments, the encapsulation layer that covers the displayunit and prevents penetration of external moisture may be formed to havea thin film encapsulation structure in which an organic film and aninorganic film are alternately stacked. In some embodiments, theencapsulation layer has a thin film encapsulation structure in which aplurality of thin films are stacked. In some embodiments, the organicfilm applied to the interface portion is spaced apart from each of theplurality of display units. In some embodiments, the organic film isformed such that a portion of the organic film directly contacts thebase substrate and a remaining portion of the organic film contacts thebarrier layer while surrounding an edge portion of the barrier layer.

In one embodiment, the OLED display is flexible and uses the soft basesubstrate formed of polyimide. In some embodiments, the base substrateis formed on a carrier substrate formed of a glass material, and thenthe carrier substrate is separated.

In some embodiments, the barrier layer is formed on a surface of thebase substrate opposite to the carrier substrate. In one embodiment, thebarrier layer is patterned according to a size of each of the cellpanels. For example, while the base substrate is formed over the entiresurface of a mother panel, the barrier layer is formed according to asize of each of the cell panels, and thus a groove is formed at aninterface portion between the barrier layers of the cell panels. Each ofthe cell panels can be cut along the groove.

In some embodiments, the method of manufacture further comprises cuttingalong the interface portion, wherein a groove is formed in the barrierlayer, wherein at least a portion of the organic film is formed in thegroove, and wherein the groove does not penetrate into the basesubstrate. In some embodiments, the TFT layer of each of the cell panelsis formed, and the passivation layer which is an inorganic film and theplanarization film which is an organic film are disposed on the TFTlayer to cover the TFT layer. At the same time as the planarization filmformed of, for example, polyimide or acryl is formed, the groove at theinterface portion is covered with the organic film formed of, forexample, polyimide or acryl. This is to prevent cracks from occurring byallowing the organic film to absorb an impact generated when each of thecell panels is cut along the groove at the interface portion. That is,if the entire barrier layer is entirely exposed without the organicfilm, an impact generated when each of the cell panels is cut along thegroove at the interface portion is transferred to the barrier layer,thereby increasing the risk of cracks. However, in one embodiment, sincethe groove at the interface portion between the barrier layers iscovered with the organic film and the organic film absorbs an impactthat would otherwise be transferred to the barrier layer, each of thecell panels may be softly cut and cracks may be prevented from occurringin the barrier layer. In one embodiment, the organic film covering thegroove at the interface portion and the planarization film are spacedapart from each other. For example, if the organic film and theplanarization film are connected to each other as one layer, sinceexternal moisture may penetrate into the display unit through theplanarization film and a portion where the organic film remains, theorganic film and the planarization film are spaced apart from each othersuch that the organic film is spaced apart from the display unit.

In some embodiments, the display unit is formed by forming thelight-emitting unit, and the encapsulation layer is disposed on thedisplay unit to cover the display unit. As such, once the mother panelis completely manufactured, the carrier substrate that supports the basesubstrate is separated from the base substrate. In some embodiments,when a laser beam is emitted toward the carrier substrate, the carriersubstrate is separated from the base substrate due to a difference in athermal expansion coefficient between the carrier substrate and the basesubstrate.

In some embodiments, the mother panel is cut in units of the cellpanels. In some embodiments, the mother panel is cut along an interfaceportion between the cell panels by using a cutter. In some embodiments,since the groove at the interface portion along which the mother panelis cut is covered with the organic film, the organic film absorbs animpact during the cutting. In some embodiments, cracks may be preventedfrom occurring in the barrier layer during the cutting.

In some embodiments, the methods reduce a defect rate of a product andstabilize its quality.

Another aspect is an OLED display including: a barrier layer that isformed on a base substrate; a display unit that is formed on the barrierlayer; an encapsulation layer that is formed on the display unit; and anorganic film that is applied to an edge portion of the barrier layer.

EXAMPLES

An embodiment of the present disclosure provides the preparation ofcompounds of Formula (I) or (II) according to the procedures of thefollowing example(s), using appropriate materials. Those skilled in theart will understand that known variations of the conditions andprocesses of the following preparative procedures can be used to preparethese compounds. Moreover, by utilizing the procedures described indetail, one of ordinary skill in the art can prepare additionalcompounds of the present disclosure.

General Information on Analytical Methods

The features of the invention will be described more specifically withreference to examples below. The materials, processes, procedures andthe like shown below may be appropriately modified unless they deviatefrom the substance of the invention. Accordingly, the scope of theinvention is not construed as being limited to the specific examplesshown below. The characteristics of samples were evaluated by using NMR(Nuclear Magnetic Resonance 500 MHz, produced by Bruker), LC/MS (LiquidChromatography Mass Spectrometry, produced by Waters), AC3 (produced byRIKEN KEIKI), High-performance UV/Vis/NIR Spectrophotometer (Lambda 950,produced by PerkinElmer, Co., Ltd.), Fluorescence Spectrophotometer(FluoroMax-4, produced by Horiba, Ltd.), Photonic multichannel analyzer(PMA-12 C10027-01, produced by Hamamatsu Photonics K.K.), Absolute PLQuantum Yield Measurement System (C11347, produced by HamamatsuPhotonics K.K.), Automatic Current voltage brightness measurement system(ETS-170, produced by System engineers co ltd), Life Time MeasurementSystem (EAS-26C, produced by System engineers co ltd), and Streak Camera(Model C4334, produced by Hamamatsu Photonics K.K.).

Example 1

The principle of the features may be described as follows for an organicelectroluminescent device as an example.

In an organic electroluminescent device, carriers are injected from ananode and a cathode to a light-emitting material to form an excitedstate for the light-emitting material, with which light is emitted. Inthe case of a carrier injection type organic electroluminescent device,in general, excitons that are excited to the excited singlet state are25% of the total excitons generated, and the remaining 75% thereof areexcited to the excited triplet state. Accordingly, the use ofphosphorescence, which is light emission from the excited triplet state,provides a high energy utilization. However, the excited triplet statehas a long lifetime and thus causes saturation of the excited state anddeactivation of energy through mutual action with the excitons in theexcited triplet state, and therefore the quantum yield ofphosphorescence may generally be often not high. A delayed fluorescentmaterial emits fluorescent light through the mechanism that the energyof excitons transits to the excited triplet state through intersystemcrossing or the like, and then transits to the excited singlet statethrough reverse intersystem crossing due to triplet-triplet annihilationor absorption of thermal energy, thereby emitting fluorescent light. Itis considered that among the materials, a thermal activation typedelayed fluorescent material emitting light through absorption ofthermal energy is particularly useful for an organic electroluminescentdevice. In the case where a delayed fluorescent material is used in anorganic electroluminescent device, the excitons in the excited singletstate normally emit fluorescent light. On the other hand, the excitonsin the excited triplet state emit fluorescent light through intersystemcrossing to the excited singlet state by absorbing the heat generated bythe device. At this time, the light emitted through reverse intersystemcrossing from the excited triplet state to the excited singlet state hasthe same wavelength as fluorescent light since it is light emission fromthe excited singlet state, but has a longer lifetime (light emissionlifetime) than the normal fluorescent light and phosphorescent light,and thus the light is observed as fluorescent light that is delayed fromthe normal fluorescent light and phosphorescent light. The light may bedefined as delayed fluorescent light. The use of the thermal activationtype exciton transition mechanism may raise the proportion of thecompound in the excited singlet state, which is generally formed in aproportion only of 25%, to 25% or more through the absorption of thethermal energy after the carrier injection. A compound that emits strongfluorescent light and delayed fluorescent light at a low temperature oflower than 100° C. undergoes the intersystem crossing from the excitedtriplet state to the excited singlet state sufficiently with the heat ofthe device, thereby emitting delayed fluorescent light, and thus the useof the compound may drastically enhance the light emission efficiency.

Example 2

The compounds of the invention can be synthesized by any method known toone of ordinary skills in the art. The compounds are synthesized fromthe commonly available starting material. The various moieties can beassembled via linear or branched synthetic routes.

Synthesis of9,9″-(5-(4,6-diphenylpyrimidin-2-yl)-1,3-phenylene)bis(9H-3,9′-bicarbazole))(Compound 1)

A mixture of 9,9″-(5-chloro-1,3-phenylene)bis((9H-3,9′-bicarbazole))(906 mg, 1.17 mmol), bis(pinacolato)diboron (297 mg, 1.17 mmol),tris(dibenzylideneacetone)dipalladium(0) (9.2 mg, 0.010 mmol), SPhos (16mg, 0.040 mmol), potassium acetate (0.191 g, 1.95 mmol) in anhydrous1,4-dioxane (5 mL) was stirred and heated at 110° C. under a nitrogenatmosphere for 2 h. Until the starting aryl halide had been completelyconsumed, 2-chloro-4,6-diphenylpyrimidine (261 mg, 0.98 mmol) indegassed 1,4-dioxane (3 mL) and potassium phosphate (1.04 g, 4.88 mmol)in degassed deionized water were added via syringe into the reactionsolution and remained heated at 110° C. for another 18 h. After allowingto room temperature, the reaction mixture was filtered through a Celitepad rinsing with CHCl₃. The filtrate was evaporated in vacuo. Theobtained residue was purified by column chromatography on silica gelusing 3:1 (v/v) hexane/chloroform as eluent to afford compound 1 as awhite solid (0.483 g, 50.8%). ¹H NMR (500 MHz, CDCl₃, δ): 9.18 (s, 2H),8.36 (s, 2H), 8.31-29 (m, 4H), 8.20-8.17 (m, 7H), 8.11 (t, J=2.0 Hz,1H), 7.85 (d, J=8.5 Hz, 2H), 7.73 (d, J=8.0 Hz, 2H), 7.64 (dd, J=8.5,2.0 Hz, 2H), 7.57-7.55 (m, 8H), 7.43-7.39 (m, 10H), 7.30 (t, J=8.0 Hz,4H).

Synthesis of9,9″-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-3,9′-bicarbazole)(Compound 2)

A mixture of 9,9″-(5-chloro-1,3-phenylene)bis((9H-3,9′-bicarbazole))(2.00 g, 2.59 mmol), bis(pinacolato)diboron (0.657 g, 2.59 mmol),tris(dibenzylideneacetone)dipalladium(0) (40 mg, 0.044 mmol), SPhos (35mg, 0.086 mmol), potassium acetate (0.423 g, 4.31 mmol) in anhydrous1,4-dioxane (10 mL) was stirred and heated at 110° C. under a nitrogenatmosphere for 3 h. Until the starting aryl halide had been completelyconsumed, 2-chloro-4,6-diphenyl-1,3,5-triazine (0.577 g, 2.16 mmol) indegassed 1,4-dioxane (5 mL) and potassium phosphate (2.29 g, 10.8 mmol)in degassed deionized water (5 mL) were added via syringe into thereaction solution and remained heated at 110° C. for another 18 h. Afterallowing to room temperature, the reaction mixture was filtered througha Celite pad rinsing with CHCl₃. The filtrate was evaporated in vacuo.The obtained residue was purified by column chromatography on silica gelusing 2:1 (v/v) hexane/chloroform as eluent to afford compound 2 as awhite solid (0.550 g, 26.3%). ¹H NMR (500 MHz, CDCl₃, δ): 9.24 (s, 2H),8.79 (d, J=7.0 Hz, 4H), 8.37 (s, 2H), 8.22 (t, J=2.0 Hz, 1H), 8.21-8.19(m, 6H), 7.84 (d, J=8.5 Hz, 2H), 7.73 (d, J=8.0 Hz, 2H), 7.67-7.62 (m,4H), 7.60-7.58 (m, 6H), 7.47-7.40 (m, 10H), 7.32-7.30 (m, 4H).

Synthesis of9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole)(Compound 3)

A mixture of 9,9′-(5-chloro-1,3-phenylene)bis(9H-carbazole) (0.60 g,1.35 mmol), bis(pinacolato)diboron (0.34 mg, 1.35 mmol),tris(dibenzylideneacetone)dipalladium(0) (10 mg, 0.011 mmol), SPhos (18mg, 0.045 mmol), potassium acetate (0.22 g, 2.26 mmol) in anhydrous1,4-dioxane (10 mL) was stirred and heated at 110° C. under a nitrogenatmosphere for 2 h. Until the starting aryl halide had been completelyconsumed, 2-chloro-4,6-diphenyl-1,3,5-triazine (303 mg, 1.13 mmol) in1,4-dioxane (5 mL) and potassium phosphate (1.20 g, 5.64 mmol) indeionized water were added via syringe into the reaction solution, andremained heated at 110° C. for another 18 h. After allowed to roomtemperature, the reaction mixture was filtered through a Celite padrinsing with toluene. The filtrate was evaporated in vacuo. The obtainedresidue was purified by column chromatography on silica gel usinghexane/chloroform as eluent to afford compound 3 as a white solid (0.41g, 55.6%).

Example 3

Preparation of Neat Films

In this example, the compound synthesised in Example 2 isvapor-deposited on a quartz substrate by a vacuum vapor depositionmethod under a condition of a vacuum degree of 10⁻³ Pa or less, so as toform a thin film having a thickness of 70 nm.

Preparation of Doped Films

The compound and host are also vapor-deposited from a separate vapordeposition source on a quartz substrate by vacuum vapor depositionmethod under a condition of a vacuum degree of 10⁻³ Pa or less, so as toform a thin film having a thickness of 100 nm and a concentration of thecompound of 20% by weight.

Evaluation of the Optical Properties

The samples were irradiated with light having a wavelength of 300 nm at300 K, and thus the light emission spectrum was measured and designatedas fluorescence. The spectrum at 77K was also measured and designated asphosphorescence. The lowest singlet energy (S1) and the lowest tripletenergy (T1) was estimated from the onset of fluorescence andphsphorescence spectrum respectively. ΔE_(ST) was calculated from theenergy gap between S1 and T1. PLQY was also measured by excitation light300 nm. The time resolved spectrum was obtained by excitation light 337nm with Streak Camera, and the component with a short light emissionlifetime was designated as fluorescent light, whereas the component witha long light emission lifetime was designated as delayed fluorescentlight. The lifetimes of the fluorescent light component (Tpron) and thedelayed fluorescent light component (Tdcay) were calculated from thedecay curves.

Preparation and Measurement of OLEDs

Thin films were laminated on a glass substrate having formed thereon ananode formed of indium tin oxide (ITO) having a thickness of 50 nm, by avacuum vapor deposition method at a vacuum degree of 1.0×10⁻⁴ Pa orless. Firstly, HAT-CN was formed to a thickness of 60 nm on ITO, andthereon TrisPCz was formed to a thickness of 30 nm. PYD2Cz was formed toa thickness of 5 nm, and thereon the compound and host were thenvapor-co-deposited from separate vapor deposition sources to form alayer having a thickness of 30 nm, which was designated as alight-emitting layer. At this time, the concentration of the compoundwas 30% by weight. SF3-TRZ was formed to a thickness of 10 nm, andthereon SF3-TRZ and Liq were vapor-co-deposited to a thickness of 30 nm.Liq was then vacuum vapor-deposited to a thickness of 2 nm, and thenaluminum (Al) was vapor-deposited to a thickness of 100 nm to form acathode, thereby producing organic electroluminescent devices andmeasured its photoelectrical properties.

Film Evaluation

PLQY (%) λ(nm) ( Max) compound 1 (20 wt % in PYD-2Cz) 490 60.7 compound2 (20 wt % in PYD-2Cz) 488 60.7 compound 3 (neat film) 455 11.7Device Evaluation

EQE (%) EQE (%) LT 90 (h) λ(nm) ( Max) ( @1000 cd) (@ 750 cd) compound 1501 12.6 9.4 3.8 compound 3 471 5.0 2.1 1

HAT-CN (60)/trisPCz (30)/PYD2Cz (5)/30 wt %-TADF:PYD2Cz (30)/SF3TRZ(10)/30 wt %-LiQ:SF3TRZ (30)/LiQ (2)

We claim:
 1. An organic light-emitting diode (OLED), comprising ananode, a cathode, and at least one organic layer comprising alight-emitting layer between the anode and the cathode, wherein thelight-emitting layer comprises: a host material; and a compound ofFormula (II) in an amount of 50% by weight or less:

wherein A is selected from

D and D′ are independently

X₁ is Ar; X₂ is selected from

Ar is independently selected from


2. The organic light-emitting diode (OLED) of claim 1, wherein thelight-emitting layer comprises the compound of Formula (II) in an amountof 20% by weight or less.
 3. The organic light-emitting diode (OLED) ofclaim 1, wherein the light-emitting layer comprises the compound ofFormula (II) in an amount of 10% by weight or less.
 4. The organiclight-emitting diode (OLED) of claim 1, wherein A is A1.
 5. The organiclight-emitting diode (OLED) of claim 1, wherein A is A2.
 6. The organiclight-emitting diode (OLED) of claim 1, wherein A is A3.
 7. The organiclight-emitting diode (OLED) of claim 1, wherein A is A4.
 8. The organiclight-emitting diode (OLED) of claim 1, wherein A is A5.
 9. The organiclight-emitting diode (OLED) of claim 1, wherein Ar is selected from Ar1,Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, and Ar10.
 10. The organiclight-emitting diode (OLED) of claim 1, wherein Ar is selected fromAr11, Ar12, Ar13, Ar14, Ar15, Ar16, Ar17, Ar18, and Ar19.
 11. Theorganic light-emitting diode (OLED) of claim 1, wherein Ar is selectedfrom Ar20, Ar21, Ar22, Ar23, and Ar24.
 12. The organic light-emittingdiode (OLED) of claim 1, wherein Ar is selected from Ar25, Ar26, andAr27.
 13. The organic light-emitting diode (OLED) of claim 1, wherein Aris selected from Ar28, Ar29, Ar30, Ar31, Ar32, Ar33, Ar34, and Ar35. 14.The organic light-emitting diode (OLED) of claim 1, wherein Ar isselected from Ar36, Ar37, Ar38, Ar39, Ar40, Ar41, Ar42, and Ar43. 15.The organic light-emitting diode (OLED) of claim 1, wherein D and D′ arethe same.
 16. The organic light-emitting diode (OLED) of claim 1,wherein D and D′ are different.
 17. The organic light-emitting diode(OLED) of claim 1, wherein the compound of Formula (II) is selected from


18. An organic light-emitting diode (OLED) of claim 1, comprising ananode, a cathode, and at least one organic layer comprising alight-emitting layer between the anode and the cathode, wherein thelight-emitting layer comprises: a host material; and a compound selectedfrom